13031-39-5Relevant articles and documents
A re-investigation of the Fries rearrangement of 3-chlorophenyl acetate and synthesis of 2-azido-1-(4-(benzyloxy)-2-chlorophenyl)ethanone from 4-bromo-3-chlorophenol
Procopiou, Panayiotis A.,Coe, Diane M.,Procopiou, George
, p. 4766 - 4768 (2017)
The Fries rearrangement of 3-chlorophenyl acetate provided the expected 4-chloro-2-hydroxy-acetophenone as the major product and 2,4-diacetyl resorcinol and 2-chloro-4-hydroxy-acetophenone as minor products. 4-Benzyloxy-2-chloroacetophenone was prepared by a Heck reaction and then elaborated to 4-benzyloxy-2-chlorophenacyl azide.
Porous coordination polymers of diverse topologies based on a twisted tetrapyridylbiaryl: Application as nucleophilic catalysts for acetylation of phenols
Seth, Saona,Venugopalan, Paloth,Moorthy, Jarugu Narasimha
, p. 2241 - 2249 (2015)
Porous coordination polymers (CPs) with partially uncoordinated pyridyl rings based on rationally designed polypyridyl linkers are appealing from the point of view of their application as nucleophilic catalysts. A D2d--symmetric tetradentate organic linker L, that is, 2,2 ',6,6'-tetramethoxy-3,3',5,5'-tetrakis(4-pyridyl)biphenyl, was designed and synthesized for metal-assisted self-assembly aimed at porous CPs. Depending on the nature of the metal ion and the counter anion, the ligand L is found to function as a 3- or 4-connecting building block leading to porous CPs of diverse topologies. The reaction of L with Zn(NO3)2 and Cd(NO3)2 yields porous 2D CPs of "fes" topology, in which the tetrapyridyl linker L serves as a 3-connecting unit with its free pyridyl rings well exposed into the pores. The functional utility of these porous CPs containing uncoordinated pyridyl rings is demonstrated by employing them as efficient heterogeneous nucleophilic catalysts for acetylation of a number of phenols with varying electronic properties and reactivities.
Effect of Solvent on the α-Effect: Nucleophilic Substitution Reactions of p-Nitrophenyl Acetate with m-Chlorophenoxide and Benzohydroxamates in MeCN-H2O Mixtures of Varying Compositions
Um, Ik-Hwan,Yoon, Hye-Won,Lee, Jeoung-Sook,Moon, Hyun-Jeung,Kwon, Dong-Sook
, p. 5939 - 5944 (1997)
Second-order rate constants have been measured spectrophotometrically for the reactions of p-nitrophenyl acetate (PNPA) with three α-effect nucleophiles, benzohydroxamate (BHA-), p- methylbenzohydroxamate (MBHA-), and p-methyl-N-methylbenzohydroxamate (M2BHA-), and a corresponding normal nucleophile, m-chlorophenoxide (ClPhO-), in MeCN-H2O mixtures of varying compositions at 25.0 °C. The reactivity of ClPhO- and M2BHA- toward PNPA decreases upon additions of MeCN into the reaction medium up to near 30-40 mol % MeCN and is followed by a gradual increase upon further additions of MeCN. BHA- and MBHA- also exhibit initial rate decreases upon the addition of MeCN up to near 40 mol % MeCN. However, unlike the ClPhO- and M2BHA- systems, the rate enhancement beyond 40 mol % MeCN is negligible for the BHA- and MBHA- systems. The present benzohydroxamates exert a large α-effect in H2O. Interestingly, BHA- and MBHA- show a decreasing α-effect trend with increasing mol % MeCN, while M2BHA- exhibits an increasing α-effect trend, indicating that the magnitude of the α-effect is significantly solvent dependent. Based on the results of the kinetic study and relative basicity measurements, the decreasing α-effect trend shown by BHA- and MBHA- has been attributed to an equilibrium shift of these hydroxamates (I) toward their isomeric structures (II or III) upon the addition of MeCN. The solvent dependent α-effect has led a conclusion that the solvent effect on the α-effect is significant; however, the ground state contribution is not solely responsible for the α-effect in the present system.
TRANSCRIPTION FACTOR BRN2 INHIBITORY COMPOUNDS AS THERAPEUTICS AND METHODS FOR THEIR USE
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Page/Page column 111, (2020/05/15)
The invention provides a variety of compounds having the structure of Formula I and uses of such compounds for treatment of various indications, including cancer as well as methods of treatment involving such compounds are also provided. The uses of the compounds may specifically include: bladder cancer, cholangiocarcinoma; colorectal cancer; diffuse large B-cell lymphoma (DLBC); liver cancer; ovarian cancer; thymoma; thyroid cancer; clear cell renal cell carcinoma (CCRCC); chromophobe renal cell carcinoma (ChRCC); prostate cancer; breast cancer; uterine cancer; pancreatic cancer; cervical cancer; uveal melanoma; acute myeloid leukemia (AML); head and neck cancer; small cell lung cancer (SCLC); lung adenocarcinoma sarcoma; mesothelioma; adenoid cystic carcinoma (ACC), sarcoma; testicular germ cell cancer; uterine cancer; pheochromocytoma and paraganglioma (PCPG); melanoma; glioma; glioblastoma multiforme; T-cell Acute Lymphoblastic Leukemia; T-cell Lympohoma, medulloblastoma; and neuroblastoma.
Novel p-functionalized chromen-4-on-3-yl chalcones bearing astonishing boronic acid moiety as MDM2 inhibitor: Synthesis, cytotoxic evaluation and simulation studies
Bhatia, Richa Kaur,Coutinho, Evans C.,Garg, Ruchika,Kancherla, Satyavathi,Kaur, Maninder,Madan, Jitender,Pissurlenkar, Raghuvir R. S.,Singh, Lakhwinder,Yadav, Manmohan
, p. 212 - 228 (2020/03/10)
Background: Novel 4-[3-(6/7/8-Substituted 4-Oxo-4H-chromen-3-yl)acryloyl]phenyl-boronic acid derivatives (5a-h) as well as other 6/7/8-substituted-3-(3-oxo-3-(4-substituted-phenyl)prop-1-enyl)-4H-chromen-4-one derivatives (3a-u) have been designed as p53-MDM2 pathway inhibitors and reported to possess significant cytotoxic properties against several cancer cell lines. Objectives: The current project aims to frame the structure-anticancer activity relationship of chromen-4-on-3-yl chalcones (3a-u/5a-h). In addition, docking studies were performed on these chromeno-chalcones in order to have an insight into their interaction possibilities with MDM2 pro-tein. Methods: Twenty-nine chromen-4-on-3-yl chalcone derivatives (3a-u/5a-h) were prepared by utilizing silica supported-HClO4 (green route with magnificent yield) and tested against four cancer cell lines (HCT116, MCF-7, THP-1, NCIH322). Results: Among the series 3a-u, compound 3b exhibited the highest anticancer activity (with IC50 values ranging from 8.6 to 28.4 μM) overall against tested cancer cell lines. Interestingly, para-Boronic acid derivative (5b) showed selective inhibition against colon cancer cell line, HCT-116 with an IC50 value of 2.35 μM. Besides the emblematic hydrophobic interactions of MDM2 inhibi-tors, derivative 5b was found to exhibit extra hydrogen bonding with GLN59 and GLN72 residues of MDM2 in molecular dynamics (MD) simulation. All the compounds were virtually nontoxic against normal fibroblast cells. Conclusion: Novel compounds were obtained with good anticancer activity especially 6-Chlorochromen-4-one substituted boronic acid derivative 5b. The molecular docking study proposed good activity as a MDM-2 inhibitor suggesting hydrophobic as well as hydrogen bonding interactions with MDM2.
Werner transition-metal complex (WTMC)-mediated mild and efficient chemo-selective acylation of phenols and anilines under solvent-free condition
Sarief, Abdulla,Haque, SK Manirul,Feroze, Syed Mudabbir,Arifuddin, Mohammed
, p. 1104 - 1109 (2018/09/27)
Werner-type transition-metal complexes (WTMC) such as [Co(NH3)5Cl]Cl2, Cu[(NH3)4]SO4, Mn(acac)3, Ni[(NH3)6]Cl2, Ni[(en)3]S2O3, and Hg[Co(SCN)4] efficiently promote the chemoselective acetylation of phenols and anilines under solvent-free condition. The results of this study clearly shows that the optimal condition for the acetylation of anilines/phenols (1 mmol) (2a–r) with acetic anhydride (1.2 mmol) in the presence of WTMC (1 mmol) and two drops of H3PO4 on heating for 10 min under solvent-free condition gives the corresponding acetanilides/phenyl acetate (3a–r) in good to excellent yield. Furthermore, the method is simple, efficient, chemoselective, and eco-friendly under solvent-free condition for the acetylation of anilines and phenols promoted by WTMC by using acetic anhydrate as the acetylating agent. The simple preparation of the catalyst, easy procedure of the acetylation reaction, and simple work-up indicate the importance of WTMC for such reactions.
Size-selective catalysts in five functionalized porous coordination polymers with unsaturated zinc centers
Deng, Dongsheng,Guo, Hui,Ji, Baoming,Wang, Weizhou,Ma, Lufang,Luo, Feng
, p. 12611 - 12616 (2017/11/06)
The five reported structural isomorphic porous coordination polymers (PCPs) 1-5, namely, [Zn(L)(ip) (1), Zn(L)(aip) (2), Zn(L)(hip) (3), Zn(L)(nip) (4), and Zn(L)(HBTC) (5) (L = N4,N4′-di(pyridine-4-yl)biphenyl-4,4′-dicarboxamide, H2ip = isophthalic acid, H2aip = 5-aminoisophthalic acid, H2hip = 5-hydroxyisophthalic acid, H2nip = 5-nitroisophthalic acid, H3BTC = 1,3,5-benzenetricarboxylic acid)] were used to catalyze the acetylation of phenol. All these heterogeneous catalysts exhibit good catalytic efficiency and size-selectivity toward the acetylation of phenols owing to their unsaturated metal centers, non-coordinated amide, and suitable channel size and shape. Among them, 2 displays the highest catalytic activity and excellent cooperative catalysis due to the presence of basic non-coordinated amide groups.
Inherent vs Apparent Chemoselectivity in the Kumada-Corriu Cross-Coupling Reaction
Hua, Xiye,Masson-Makdissi, Jeanne,Sullivan, Ryan J.,Newman, Stephen G.
supporting information, p. 5312 - 5315 (2016/11/02)
The Kumada-Corriu reaction is a powerful tool for C-C bond formation, but is seldom utilized due to perceived chemoselectivity issues. Herein, we demonstrate that high-yielding couplings can occur in the presence of many electrophilic and heterocyclic functional groups. Our strategy is mechanically based, matching oxidative addition rates with the rate of syringe pump addition of the Grignard reagent. The mechanistic reason for the effectiveness of this strategy is uncovered by continuous-infusion ESI-MS studies.
Palladium-Catalyzed Desilylative Acyloxylation of Silicon-Carbon Bonds on (Trimethylsilyl)arenes: Synthesis of Phenol Derivatives from Trimethylsilylarenes
Gondo, Keisuke,Oyamada, Juzo,Kitamura, Tsugio
supporting information, p. 4778 - 4781 (2015/10/12)
A strategy for desilylative acetoxylation of (trimethylsilyl)arenes has been developed in which (trimethylsilyl)arenes are converted into acetoxyarenes. The direct acetoxylation is performed in the presence of 5 mol % of Pd(OAc)2 and PhI(OCOCF3)2 (1.5 equiv) in AcOH at 80°C for 17 h. The acetoxyarenes are obtained in good to high yields (67-98%). The synthetic utility is demonstrated with a one-pot transformation of (trimethylsilyl)arenes to phenols by successive acetoxylation and hydrolysis. Furthermore, desilylative acyloxylation of 2-(trimethylsilyl)naphthalene using several carboxylic acids has been conducted.
Steric control of site selectivity in the Pd-catalyzed C-H acetoxylation of simple arenes
Cook, Amanda K.,Emmert, Marion H.,Sanford, Melanie S.
supporting information, p. 5428 - 5431 (2013/11/19)
This report describes the use of an oxidant and a ligand to control site selectivity in the Pd(OAc)2-catalyzed C-H acetoxylation of simple arenes. The use of MesI(OAc)2 as the terminal oxidant in combination with acridine as the ligand results in primarily sterically controlled selectivity. In contrast, with Pd(OAc)2 as the catalyst and PhI(OAc)2 as the oxidant, electronic effects dominate the selectivity of arene C-H acetoxylation.
