- Iron-catalyzed tandem oxidative coupling and acetal hydrolysis reaction to prepare formylated benzothiazoles and isoquinolines
-
The aldehyde group is one of the most versatile intermediates in synthetic chemistry, and the introduction of an aldehyde group into heteroarenes is important for the transformation of molecular structure. Herein, we achieved the direct formylation of benzothiazo/les and isoquinolines. The reaction features a novel iron-catalyzed Minisci-type oxidative coupling process using commercially available 1,3-dioxolane as a formylated reagent followed by acetal hydrolysis without a separation process. The reaction can be performed under exceedingly mild reaction conditions and exhibits broad functional group tolerance.
- Wu, Yue,Guo, Peng,Chen, Long,Duan, Weijie,Yang, Zengzhuan,Wang, Tao,Chen, Ting,Xiong, Fei
-
supporting information
p. 3271 - 3274
(2021/04/07)
-
- Photoinduced remote heteroaryl migration accompanied by cyanoalkylacylation in continuous flow
-
A photoinduced 1,4-heteroaryl migration from a carbon center to a nitrogen center accompanied by a cyanoalkylacylation of heterocyclic-substituted azidyl homoallylic alcohols and cycloketone oxime esters has been described. This simple and powerful protoc
- Duan, Xiu,Guo, Kai,Liu, Jie,Ma, Can-Liang,Qin, Long-Zhou,Qiu, Jiang-Kai,Sun, Qi,Wu, Meng-Yu,Yuan, Xin,Zhang, Xin-Peng,Zhu, Shan-Shan
-
supporting information
p. 8916 - 8921
(2021/11/27)
-
- Overcoming Electron-Withdrawing and Product-Inhibition Effects by Organocatalytic Aerobic Oxidation of Alkylpyridines and Related Alkylheteroarenes to Ketones
-
An organocatalyzed aerobic benzylic C-H oxidation of alkyl and aryl heterocycles has been developed. This transition metal-free method is able to overcome the electron-withdrawing effect as well as product-inhibition effects in heterobenzylic radical oxidation. A variety of ketones bearing N-heterocyclic groups could be prepared under relatively mild conditions with moderate to high yields.
- Wang, Hua,Liu, Jie,Qu, Jian-Ping,Kang, Yan-Biao
-
p. 3942 - 3948
(2020/03/23)
-
- Neutral analogs of the heat shock protein 70 (Hsp70) inhibitor, JG-98
-
The heat shock protein 70 (Hsp70) family of molecular chaperones are highly expressed in tumors. Inhibitors containing a pyridinium-modified benzothiazole, such as JG-98, bind to a conserved, allosteric site in Hsp70, showing promising anti-proliferative activity in cancer cells. When bound to Hsp70, the charged pyridinium makes favorable contacts; however, this moiety also increases the inhibitor's fluorescence, giving rise to undesirable interference in biochemical and cell-based assays. Here, we explore whether the pyridinium can be replaced with a neutral pyridine. We report that pyridine-modified benzothiazoles, such as compound 17h (JG2-38), have reduced fluorescence, yet retain promising anti-proliferative activity (EC50 values ~0.1 to 0.07 μM) in breast and prostate cancer cell lines. These chemical probes are expected to be useful in exploring the roles of Hsp70s in tumorigenesis and cell survival.
- Gestwicki, Jason E.,Shao, Hao
-
-
- Preparation method of thiabendazole intermediate
-
The invention provides a preparation method of a thiabendazole intermediate. The method uses a raw material containing o-phenylenediamine to prepare the thiabendazole intermediate shown as a formula (1), and comprises the following steps: in an acidic environment, carrying out condensation reaction on the raw material containing o-phenylenediamine to obtain a crude product 1; carrying out halogenation reaction on the crude product 1 to obtain a crude product 2; and carrying out decarboxylation reaction on the crude product 2, and purifying to obtain the thiabendazole intermediate. According tothe invention, the method is low in raw material cost, simple in synthetic route, inapplicable to catalysts, recyclable in solvent, almost zero in emission of three wastes, mild in reaction condition, simple to operate and suitable for modern industrial production, and the influence on the environment is avoided, and the yield is as high as 80% or above. R is Cl or Br.
- -
-
Paragraph 0034-0035
(2020/12/31)
-
- Metal-free C-H methylation and acetylation of heteroarenes with PEG-400
-
The generation of a methyl carbon source from renewable and cheap sources is challenging. Herein, we describe a novel and an efficient route for methylation and acetylation of aza-heteroarenes using PEG-400 under O2and TsOH·H2O for the first time by tuning the reaction conditions using a different set of starting materials. The key features of the current protocol are oxidative C-O and C-C bond scission under metal-free conditions with good functional group tolerance, and a broad substrate scope. The potential applicability of the designed methodology was demonstrated for the synthesis of central nervous system (CNS) depressant and anticonvulsant drug molecules by a one-pot strategy.
- Kudale, Vishal Suresh,Wang, Jeh-Jeng
-
supporting information
p. 3506 - 3511
(2020/06/25)
-
- Carbonylative Acetylation of Heterocycles
-
Herein, a new procedure for the carbonylative acetylation of heterocycles has been developed. In this process, organic peroxide acts as the methyl source. Various heterocycles were transformed into the corresponding methyl heterocyclic ketones in moderate to good yields.
- Zhang, Youcan,Yin, Zhiping,Wu, Xiao-Feng
-
supporting information
p. 213 - 216
(2020/01/22)
-
- Method for synthesizing benzothiazole by microwave radiation of benzothioamide compound in aqueous phase
-
The invention discloses a method for synthesizing benzothiazole by microwave radiation of a benzothioamide compound in an aqueous phase. The method includes the steps: adding the benzothioamide compound into the aqueous phase under microwave conditions; performing cyclization under alkaline conditions to generate the benzothiazole. The method for preparing the benzothiazole is environmentally friendly, simple and convenient in operation, safe, cheap and efficient. Compared with the prior art, the method is applicable to a lot of functional groups, high in yield, few in by-products, simple in operation, safe, low in cost and environmentally friendly.
- -
-
Paragraph 0013; 0063
(2019/02/13)
-
- Iron-Catalyzed Minisci Type Acetylation of N-Heteroarenes Mediated by CH(OEt)3/TBHP
-
Iron-catalyzed acetylation of electron deficient N-heteroarenes has been reported using triethylorthoformate as robust and inexpensive acetyl source. This new method is successfully applied for the acetylation of quinolines, isoquinoline, quinoxalines, arylpyridines, bipyridines, and benzothiazole.
- Srinivasulu,Shantharjun,Vani,Ashalu, K. Chinna,Mohd,Wencel-Delord,Colobert,Reddy, K. Rajender
-
supporting information
p. 1815 - 1819
(2019/02/20)
-
- Iron-catalyzed Minisci acylation of N-heteroarenes with α-keto acids
-
An efficient and mild protocol has been developed for the Minisci acylation reactions of nitrogen-containing heteroarenes with α-keto acids. Distinct from the conventional Minisci acylation conditions, the chemistry was performed using non-noble metal Fe(II), instead of expensive Ag(I) salt, as catalyst. A wide range of substrates, including aliphatic or aromatic α-keto acids, as well as various N-heteroarenes, proved to be compatible with the protocol. Scale-up experiment also demonstrates the practicality of the approach.
- Wang, Xiu-Zhi,Zeng, Cheng-Chu
-
supporting information
p. 1425 - 1430
(2019/02/01)
-
- A benzothiazole - triazole - isatin compound and its synthesis and use (by machine translation)
-
The invention discloses a benzothiazole - triazole - isatin compound and its synthesis and use thereof, the preparation method is: through 2 - amino thiophenol, [...] preparation 1 - (benzo [d] thiazole - 2 - yl) b - 1 - ol, then mixing it with chromium trioxide in round-bottom flask is prepared 1 - (benzo [d] thiazole - 2 - yl) b - 1 - one; and then with the N - bromosuccinimide, paratoluene sulfonic acid is placed in a round-bottom flask, adding acetonitrile, to obtain 1 - (benzo [d] thiazole - 2 - yl) - 2 - bromo b - 1 - one; and then and sodium azide in round-bottom flask, adding tetrahydrofuran, to obtain the product of re-with the substituted 1 - (c - 2 - alkyne - 1 - yl) indoline - 2, 3 - dione, vitamin C sodium, five water copper sulfate is placed in round-bottom flask, add DMF, shall be benzothiazole - triazole - isatin compound. Preparation method of this invention the step is simple, easy to operate, the preparation of the benzothiazole - triazole - isatin compound to α - glucosidase has better inhibition activity, for the antidiabetic drug development and application provides new selection. (by machine translation)
- -
-
Paragraph 0024; 0027
(2018/09/08)
-
- Silver-mediated 2-arylation/alkylation/acylation of benzothiazoles with aldehydes in water
-
An efficient and environmentally benign method was developed for the facile synthesis of various 2-aryl and 2-alkyl substituted benzothiazoles in moderate to good yields, using a silver-mediated redox condensation of benzothiazoles and aldehydes in water. Furthermore, this method is also applicable to prepare 2-acyl benzothiazoles.
- Hua, Min,Wang, Chunqin,Liu, Qixing,Chen, Danyi,Fu, Hao,Zhou, Haifeng
-
p. 1226 - 1237
(2018/08/06)
-
- CYCLIC SULFAMIDE COMPOUNDS AND METHODS OF USING SAME
-
The present disclosure provides, in part, cyclic sulfamide compounds, and pharmaceutical compositions thereof, useful as modulators of Hepatitis B (HBV) core protein, and methods of treating Hepatitis B (HBV) infection.
- -
-
Page/Page column 348
(2018/09/21)
-
- Compositions containing five-membered unsaturated heterocyclic structure of the α, β unsaturated ketone compound and its preparation method and application
-
The invention provides alpha, beta unsaturated ketone compounds containing benzo five-membered unsaturated heterocycle structures as well as a preparation method and an application and use of the compounds. The alpha, beta unsaturated ketone compounds containing the benzo five-membered unsaturated heterocycle structures have the structure of a formula (I). In addition, the invention further provides a method for preparing the compounds and a pharmaceutical composition containing the components as active components. In vitro activity tests show that the compounds provided by the invention show a remarkable inhibiting effect on tumor cells. Therefore, the invention lays a foundation for lucubrating and developing anti-tumor medicines in the future and meanwhile further provides a new technical means for treating tumor diseases.
- -
-
Paragraph 0188
(2017/07/14)
-
- Catalytic Aerobic Photo-oxidation of a Methyl Group on a Heterocycle to Produce an Aldehyde via Homolytic C-I Bond Cleavage caused by Irradiation with Visible Light
-
A new catalytic method was developed for photo-oxidizing the methyl group on aromatic heterocycles such as benzothiazole, benzoxazole, and quinoline to produce the corresponding aldehyde. This is the first report of the metal-free catalytic synthesis of benzothiazole-2-carboxaldehydes using molecular oxygen as the terminal oxidant.
- Nagasawa,Tachikawa,Yamaguchi,Tada,Miura,Itoh
-
supporting information
p. 178 - 182
(2016/02/14)
-
- Design, synthesis and biological evaluation of novel benzimidazole-2-substituted phenyl or pyridine propyl ketene derivatives as antitumour agents
-
A series of novel benzimidazole-2-subsituted phenyl or pyridine propyl ketene derivatives were designed and synthesized. The biological activities of these derivatives were then evaluated as potential antitumour agents. These compounds were assayed for growth-inhibitory activity against HCT116, MCF-7 and HepG2 cell lines in vitro. The IC50 values of compounds A1 and A7 against the cancer cells were 0.06e3.64 mM and 0.04e9.80 mM, respectively. Their antiproliferative activities were significantly better than that of 5-Fluorouracil (IC50: 56.96e174.50 mM) and were close to that of Paclitaxel (IC50: 0.026 e1.53 μ M). The activity of these derivatives was over 100 times more effective than other reported structures of chalcone analogues (licochalcone A). A preliminary mechanistic study suggested that these compounds inhibit p53-MDM2 binding. Compounds A1, A7 and A9 effectively inhibited tumour growth in BALB/c mice with colon carcinoma HCT116 cells. The group administered 200 mg/kg of compound A7 showed a 74.6% tumour growth inhibition with no signs of toxicity at high doses that was similar to the inhibition achieved with the 12.5 mg/kg irinotecan positive control (70.2%). Therefore, this class of benzimidazole-2-subsituted phenyl or pyridine propyl ketene derivatives represents a promising lead structure for the development of possible p53-MDM2 inhibitors as new antitumour agents.
- Wu, Lin-Tao,Jiang, Zhi,Shen, Jia-Jia,Yi, Hong,Zhan, Yue-Chen,Sha, Ming-Quan,Wang, Zhen,Xue, Si-Tu,Li, Zhuo-Rong
-
p. 328 - 336
(2016/04/05)
-
- Chloroacetate-promoted selective oxidation of heterobenzylic methylenes under copper catalysis
-
The efficient selective oxidation and functionalization of C-H bonds with molecular oxygen and a copper catalyst to prepare the corresponding ketones was achieved with ethyl chloroacetate as a promoter. In this transformation, various substituted N-heterocyclic compounds were well tolerated. Preliminary mechanistic investigations indicated that organic radical species were involved in the overall process. The N-heterocyclic compounds and ethyl chloroacetate work synergistically to activate C-H bonds in the methylene group, which results in the easy generation of free radical intermediates, thus leading to the corresponding ketones in good yields.
- Liu, Jianming,Zhang, Xin,Yi, Hong,Liu, Chao,Liu, Ren,Zhang, Heng,Zhuo, Kelei,Lei, Aiwen
-
supporting information
p. 1261 - 1265
(2015/01/30)
-
- NEW ARYLALKENYLPROPARGYLAMINE DERIVATIVES EXHIBITING NEUROPROTECTIVE ACTION FOR THE TREATMENT OF NEURODEGENERATIVE DISEASES
-
The invention relates to novel arylalkenylpropargylamine derivatives of general formula (I) or enantiomers or diastereomers thereof or salts, optionally pharmaceutically acceptable salts, or solvates of any of these. The compounds can be used in treating or preventing a disease or condition in a mammal related to monoamine oxidase dysfunction, especially in neurodegenerative diseases, e.g. Parkinson's disease, Alzheimer's disease or Huntington's disease.
- -
-
Page/Page column 38
(2015/06/25)
-
- Rhodium Catalyzed Asymmetric Hydrogenation of 2-Pyridine Ketones
-
Catalyzed by [Rh(COD)Binapine]BF4, the asymmetric hydrogenation of 2-pyridine ketones has been achieved with excellent enantioselectivities (enantiomeric excesses up to 99%) under mild conditions. This method is suitable for various kinds of 2-pyridine ketones and their derivatives. A number of enantiomerically pure chiral 2-pyridine-aryl/alkyl alcohols were prepared through hydrogenation, which can be used directly in organic synthesis.
- Yang, Hailong,Huo, Ningning,Yang, Ping,Pei, Hao,Lv, Hui,Zhang, Xumu
-
supporting information
p. 4144 - 4147
(2015/09/15)
-
- Peroxides as "switches" of dialkyl H-phosphonate: Two mild and metal-free methods for preparation of 2-acylbenzothiazoles and dialkyl benzothiazol-2-ylphosphonates
-
Two mild and metal-free methods for the preparation of two kinds of important benzothiazole derivatives, 2-acylbenzothiazoles and dialkyl benzothiazol-2-ylphosphonates, respectively, were developed. The dialkyl H-phosphonate (RO)2P(O)H exists i
- Chen, Xiao-Lan,Li, Xu,Qu, Ling-Bo,Tang, Yu-Chun,Mai, Wen-Peng,Wei, Dong-Hui,Bi, Wen-Zhu,Duan, Li-Kun,Sun, Kai,Chen, Jian-Yu,Ke, Dian-Dian,Zhao, Yu-Fen
-
p. 8407 - 8416
(2015/03/18)
-
- Chemoenzymatic synthesis of (R)- and (S)-1-heteroarylethanols
-
A chemoenzymatic methodology for the synthesis of highly enantiomerically enriched (S)- and (R)-1-heteroarylethanols by enantioselective bioreduction with baker's yeast of the corresponding 1-heteroarylethanones followed by three racemization free chemical steps including a Mitsunobu reaction was developed.
- Tosa, Monica Ioana,Podea, Paula Veronica,Paizs, Csaba,Irimie, Florin Dan
-
p. 2068 - 2071
(2008/12/22)
-
- THIAZOLES USEFUL AS INHIBITORS OF PROTEIN KINASES
-
The present invention relates to compounds useful of inhibitors of protein kinases. The invention also provides pharmaceutically acceptable compositions comprising said compounds and methods of using the compositions in the treatment of various disease, conditions, or disorders.
- -
-
-
- Reactions of heterocumulenes with organometallic reagents: VIII. Reactions of carbanions derived from alkoxy- and alkylsulfanylethenes with isothiocyanates - A convenient route to 2-propenethioamides, 1-methylsulfanyl-2-propen-1- imines, and benzothiazole
-
Metalated alkoxy- and alkylsulfanylethenes readily add to isothiocyanates; the subsequent hydrolysis or alkylation of the adducts leads to formation of 2-propenethioamides or 1-methylsulfanyl-2-propen-1-imines (as mixtures of syn and anti isomers) in 74-1
- Nedolya,Shlyakhtina,Sarapulova,Brandsma
-
-
- Studies on isocyanides. 2-Isocyanothioanisole, a synthetic equivalent of the benzothiazol-2-YL anion
-
A synthesis of 2-isocyanothioanisole (3) is described. The reaction between 3 and electrophilic reagents took place easily to give 2-functionalized benzothiazoles (6).
- Bossio, Ricardo,Marcaccini, Stefano,Pepino, Roberto,Torroba, Tomas
-
p. 471 - 474
(2007/10/03)
-
- General Reactivity of 2-Lithiobenzothiazole to Various Electrophiles and the Use as a Formyl Anion Equivalent in the Synthesis of α-Hydroxy Carbonyl Compounds
-
The reaction of 2-lithiobenzothiazole with a variety of electrophiles such as aldehydes, ketones, carboxylic esters, lactones, nitriles, and amides afforded the expected addition and substitution products.Trimethylsilyl chloride readily reacted with the b
- Chikashita, Hidenori,Ishibaba, Megumi,Ori, Keiji,Itoh, Kazuyoshi
-
p. 3637 - 3648
(2007/10/02)
-
- Synthesis and Application of Imidazole Derivatives. Synthesis and Acyl Activation of 2-Acyl-1-methyl-1H-imidazoles
-
2-Acyl-1-methyl-1H-imidazoles (3) were prepared in good yields by treating 1-acylpyrrolidines (5) with 2-lithio-1-methyl-1H-imidazole (2) at -78 deg C.The acyl group of 3 was very stable under various severe conditions, but 2-benzoylimidazole (3a) was gradually hydrolyzed by heating with 1.3 N NaOH to produce benzoic acid and 1-methyl-1H-imidazole.Acyl activation of 3 was performed by direct quaternization of 3 with iodomethane or dimethyl sulfate or more successfully by quaternization of the corresponding O-trimethylsilylated gem-cyanohydrin (11) with dimethyl sulfate.Keywords- acylimidazole; 2-acylimidazole; imidazolium salt; acyl group activation; acylation; C-C bond fission; protecting group; latent functionality
- Ohta, Shunsaku,Hayakawa, Satoshi,Moriwaki, Hiroki,Harada, Suzumi,Okamoto, Masao
-
p. 4916 - 4926
(2007/10/02)
-
- SYNTHESIS OF 2-ACYL-1-METHYL-1H-IMIDAZOLES AND REACTIVITY OF THE ACYL GROUP
-
2-Alkanoyl- and 2-aroyl-1-methyl-1H-imidazoles (3) were prepared in good yields by treating 1-acylpyrrolidine (1) with 2-lithio-1-methyl-1H-imidazole (2) at -78 deg C.Although 2-benzoyl-1-methyl-1H-imidazole (3a) was stable under n-Pr-NH2/80 deg C/10 h; 2percent K2CO3/aq.CH3OH/80 deg C/10 h; 20percent H2SO4/80 deg C/10 h; CF3COOH/r.t./17 h, it was hydrolysed into benzoic acid and 1-methyl-1H-imidazole by heating in 1.3 N-NaOH - aq. ethanol at 80 deg C for 30 h.The acyl group of 3 was activated by conversion to the corresponding imidazolium salt (4), which could react with various nucleophiles.
- Ohta, Shunsaku,Hayakawa, Satoshi,Moriwaki, Hiroki,Tsuboi, Shin-ichi,Okamoto, Masao
-
p. 1759 - 1764
(2007/10/02)
-
- 1,3-vs- 1,5-DIPOLAR REACTIVITY OF 1-PHENYLMETHYL-4N-ACETYLIMINO-1H-1,2,4-TRIAZOLIUM BETAIN TOWARD AROMATIC ISOTHIOCYANATES
-
The title betain I was found to display both 1,3- and 1,5-dipolar reactivity, depending on reaction conditions.Whereas the reaction with aromatic isothiocyanates in nonpolar solvents produced cycloadducts in concerted manner stepwise addition in dimethylf
- Zalupsky, Peter,Martvon, Augustin
-
p. 1713 - 1721
(2007/10/02)
-