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Nitration of aromatics with dinitrogen pentoxide in a liquefied 1,1,1,2-tetrafluoroethane medium
Regardless of the sustainable development path, today, there are highly demanded chemical productions still operating that bear environmental and technological risks inherited from the previous century. The fabrication of nitro compounds, and nitroarenes in particular, is traditionally associated with acidic wastes formed in nitration reactions exploiting mixed acids. However, nitroarenes are indispensable for industrial and military applications. We faced the challenge and developed a greener, safer, and yet effective method for the production of nitroaromatics. The proposed approach comprises the application of an eco-friendly nitrating agent, namely dinitrogen pentoxide (DNP), in the medium of liquefied 1,1,1,2-tetrafluoroethane (TFE) - one of the most non-hazardous Freons. Importantly, the used TFE is not emitted into the atmosphere but is effortlessly recondensed and returned into the process. DNP is obtainedviathe oxidation of dinitrogen tetroxide with ozone. The elaborated method is characterized by high yields of the targeted nitro arenes, mild reaction conditions, and minimal amount of easy-to-utilize wastes.
Fauziev, Ruslan V.,Kharchenko, Alexandr K.,Kuchurov, Ilya V.,Zharkov, Mikhail N.,Zlotin, Sergei G.
p. 25841 - 25847
(2021/08/09)

Polyfluoroalkyl-containing isoindolinone benzamide derivative, preparation method and application thereof
The invention provides a polyfluoroalkyl-containing isoindolinone benzamide derivative, which has the following general formula A-1 as shown in the specification, wherein substituent groups are shown as the specification. The polyfluoroalkyl-containing isoindolinone benzamide derivative provided by the invention is suitable for agricultural insecticide.
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Paragraph 0122-0125

(2021/05/12)

Light-induced carboxylation of aryl derivatives with cooperative COF as an active photocatalyst and Ni(ii) co-catalyst
The photocatalytic carboxylation of aryl derivatives was demonstrated under CO2at atmospheric pressure using a mesoporous covalent organic framework (COF) as the active photocatalyst with triethylamine (TEA) as a sacrificial electron source under visible light. A yield of greater than 91% of the isolated product was achieved with 5 mg of catalyst. The reaction cycle is dependent on the use of the Ni(dmg)2co-catalyst and the sacrificial electron donor (TEA). The reaction does not occur in the absence of light (445 nm) even at elevated reaction temperature. We have also demonstrated that a yield of 32% of the isolated product could be obtained with the use of sunlight in the catalytic cycle. Additionally, this heterogeneous catalytic system was recyclable and reusable for several cycles.
Chakrabortty, Pekham,Das, Anjan,Chowdhury, Arpita Hazra,Ghosh, Swarbhanu,Khan, Aslam,Islam, Sk. Manirul
p. 4738 - 4745
(2021/03/22)

Br?nsted acid-catalyzed chlorination of aromatic carboxylic acids
The chlorination of aromatic carboxylic acids with SOCl2 has been effectively performed by reacting with a Br?nsted acid as the catalyst. Based on this discovery, an efficient catalytic method that is cheaper than traditional catalytic methods was developed. 20 substrates were chlorinated offering excellent yields in a short reaction time. And the SOCl2/Br?nsted acid system has been used in a larger scale preparative reaction. A dual activation mechanism was proposed to prove the irreplaceable system of SOCl2/Br?nsted acid.
Yu, Zhiqun,Yao, Hongmiao,Xu, Qilin,Liu, Jiming,Le, Xingmao,Ren, Minna
supporting information
p. 685 - 689
(2021/04/09)

From off-to on-target: New BRAF-inhibitor-template-derived compounds selectively targeting mitogen activated protein kinase kinase 4 (MKK4)
The mitogen-activated protein kinase (MAP) kinase 4 (MKK4) was found to be a major regulator of liver regeneration and could be a valuable drug target addressing liver related diseases by restoring its intrinsic regenerative capacity. We report on the synthesis and optimization of novel MKK4 inhibitors following a target-hopping strategy from the FDA-approved BRAFV600E inhibitor PLX4032 (8). Applying an iterative multi-parameter optimization process we carved out essential structural features yielding in compounds with a low nanomolar affinity for MKK4 and excellent selectivity profiles against the main off-targets MKK7 and JNK1, which, upon relevant inhibition, would totally abrogate the pro-regenerative effect of MKK4 inhibition, as well as against the off-targets MAP4K5, ZAK and BRAF with selectivity factors ranging from 40 to 430 for our best-balanced compounds 70 and 73.
Kl?vekorn, Philip,Pfaffenrot, Bent,Juchum, Michael,Selig, Roland,Albrecht, Wolfgang,Zender, Lars,Laufer, Stefan A.
supporting information

(2020/11/20)

Indolone derivative and pharmaceutical application thereof
The invention provides an indolone derivative and pharmaceutical application thereof. The structure of the indolone derivative is shown as a formula (A). Experimental results show that the compound provided by the invention has obviously improved pharmacokinetic properties than BIBF1120, has excellent inhibition effects on VEGFR, FGFR and PDGFR, can be used as a VEGFR, FGFR and/or PDGFR inhibitor,an angiogenesis inhibitor and a drug for preventing and/or treating various tumors including pharyngeal squamous cell carcinoma, and has a wide application prospect.
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Paragraph 0040-0046

(2021/03/31)

Novel phenolic Mannich base derivatives: synthesis, bioactivity, molecular docking, and ADME-Tox Studies
In this study, it was aimed to synthesize novel molecules containing potential biological active phenolic Mannich base moiety and evaluate the inhibition properties against α-glycosidase (α-Gly) and acetylcholinesterase (AChE). For this purpose, phenolic aldehydes (1–3) were synthesized from 4-hydroxy-3-methoxy benzaldehyde (vanillin) according to the Mannich Reaction. Five different carboxylic acid hydrazides (4a-e) were synthesized from esters obtained from carboxylic acids. Fifteen Schiff base derivatives (5a-e, 6a-e, and 7a-e) were synthesized from the condensation reaction of compounds 1–3 with 4a-e. In this work, a series of novel Schiff bases from Phenolic Mannich bases (5a-e, 6a-e, and 7a-e) were tested toward α-Gly and AChE enzymes. Compounds 5a-e, 6a-e, and 7a-e showed Kis in ranging of 341.36 ± 31.84–904.76 ± 93.56?nM on AChE and 176.27 ± 22.87—621.77 ± 69.98?nM on α-glycosidase. Finally, novel compounds were found using molecular docking method to calculate the biological activity of these bases against many enzymes. The enzymes used in these calculations are acetylcholinesterase and α-glycosidase, respectively. Molecule 6b is more effective and active than other molecules with a docking score parameter value of ? 8.77 against AChE enzyme and 6d is more effective and active than other molecules with a docking score parameter value of ? 4.94 against α-Gly enzyme. After calculating the biological activities of novel compounds, ADME/T analysis parameters were examined to calculate the future drug use properties.
?endil, K?v?lc?m,Demircio?lu, ?brahim Hakk?,Gül?in, ?lhami,Taslimi, Parham,Tokal?, Feyzi Sinan,Tuzun, Burak
(2021/07/12)

Antibacterial and Antiviral Activities of 1,3,4-Oxadiazole Thioether 4H-Chromen-4-one Derivatives
Various 1,3,4-oxadiazole thioether 4H-chromen-4-one derivatives were conceived. The title compounds demonstrated striking inhibitory effects againstXac,Psa, andXoo. EC50data exhibited that A8 (19.7 μg/mL) had better antibacterial activity againstXoothan myricetin, BT, and TC. Simultaneously, the mechanism of action of A8 had been verified by SEM. The results of anti-tobacco mosaic virus indicated that A9 had the bestin vivoantiviral effect compared with ningnanmycin. From the data of MST, it could be seen that A9 (0.003 ± 0.001 μmol/L) exhibited a strong binding capacity, which was far superior to ningnanmycin (2.726 ± 1.301 μmol/L). This study shows that the 1,3,4-oxadiazole thioether 4H-chromen-4-one derivatives may become agricultural drugs with great potential.
Cao, Xiao,Liu, Fang,Liu, Liwei,Liu, Tingting,Peng, Feng,Wang, Qifan,Xie, Chengwei,Xue, Wei,Yang, Jinsong
p. 11085 - 11094
(2021/10/01)

Mild Copper-Catalyzed Addition of Arylboronic Esters to Di- tert -butyl Dicarbonate: An Easy Access to Methyl Arylcarboxylates
An efficient copper-catalyzed addition of arylboronic esters to (Boc) 2O was developed. The reaction can be conducted under exceedingly mild conditions and is compatible with a variety of synthetically relevant functional groups. It therefore represents a useful alternative route for the synthesis of methyl arylcarboxylates. A preliminary mechanistic study indicated the involvement of an addition-elimination mechanism.
Xu, Jin-Di,Su, Xiao-Bo,Wang, Cai,Yao, Li-Wei,Liu, Jing-Hui,Hu, Guo-Qin
supporting information
p. 833 - 837
(2021/02/26)

The Suzuki–Miyaura Cross-Coupling as the Key Step in the Synthesis of 2-Aminobiphenyls and 2,2'-Diaminobiphenyls: Application in the Synthesis of Schiff Base Complexes of Zn
2-Nitrophenylboronic acids serve as interesting starting materials for the construction of biphenyl- and terphenyl-based amines if subjected to the Suzuki–Miyaura reaction. Unfortunately, these boronic acids suffer from low reactivity in Suzuki reactions, alongside their low stability in the presence of Pd. Herein, a general method for the construction of 2-nitro-substituted bi- and terphenyls is presented, with special emphasis on the synthesis of 2-amino-2'-nitrobi- and terphenyls. Comparisons are made with other boronic acids that have some of the aforementioned issues. Finally, the application of the obtained 2-amino-2'-nitrobi- and terphenyls as starting materials for the synthesis of bi- and terphenyl based di- and triamines is encountered for, with emphasis on the use of these amines as precursors for Schiff base ligands. In addition, the synthesis of some Zn complexes of these ligands is presented.
Hylland, Knut Tormodss?nn,?ien-?degaard, Sigurd,Tilset, Mats
supporting information
p. 4208 - 4226
(2020/07/06)

NITRATION
The present invention relates to a process for preparing a nitrated compound, comprising the step of reacting a compound (A) comprising at least one substituted or unsubstituted aromatic or heteroaromatic ring, wherein said heteroaromatic ring comprises at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphor, selenium and nitrogen, with a compound of formula (I) wherein Y is selected from the group consisting of hydrogen and nitro.
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Page/Page column 36; 37; 47; 66-67; 43; 49; 70

(2020/05/28)

Palladium-Catalyzed Chlorocarbonylation of Aryl (Pseudo)Halides Through In Situ Generation of Carbon Monoxide
An efficient palladium-catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high-value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl-containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO.
Bismuto, Alessandro,Boehm, Philip,Morandi, Bill,Roediger, Sven
supporting information
p. 17887 - 17896
(2020/08/19)

Oxidative Esterification of Aldehydes and Alcohols Catalyzed by Camphor-Based Imidazolium Salts
Abstract: Sixteen new camphor-based imidazolium salts have been synthesized with renewable camphorsulfonic acid as the starting material. The chemical shifts of the characteristic proton of C2 on the imidazolium ring (N?C=N) were discussed thoroughly and all of these imidazolium salts exhibit good thermal stability. Furthermore, the excellent catalytic performance of the synthesized imidazolium salts were observed in the oxidative esterification between aromatic or aliphatic aldehydes containing electron-withdrawing or electron-donating groups on aromatic ring and primary or secondary alcohol by air as the sole oxidant. Graphic Abstract: [Figure not available: see fulltext.].
Bian, Tiancen,Feng, Li,Li, Danfeng,Huang, Jiaxin,Zhao, Yuxun,Xu, Xu,Yang, Yiqin,Wang, Shifa
p. 1812 - 1820
(2020/01/11)

Aromatic acyl hydrazone derivative and application thereof as NA inhibitor
The invention relates to an aromatic acyl hydrazone derivative as shown in a structural formula I, pharmaceutically acceptable salt and a pharmaceutical composition thereof, and application of the aromatic acyl hydrazone derivative and the pharmaceutically acceptable salt and the pharmaceutical composition in preparation of an influenza virus neuraminidase inhibitor, wherein R is one of trifluoromethyl, nitryl, 3-methyl-4-nitryl, 3-hydroxyl-4-nitryl, 3-nitryl-4-hydroxyl, hydroxyl, dihydroxyl, dinitryl, 3-methoxy-4-hydroxyl or trihydroxyl; Y is selected from hydroxyl, dihydroxyl, 2-hydroxyl-3-methoxy, 2-hydroxyl-4-methoxy,2-hydroxyl-5-methoxy,2-hydroxyl-6-methoxy,3-hydroxyl-2-methoxy,3-hydroxyl-4-methoxy,3-hydroxyl-5-methoxy,3-hydroxyl-6-methoxy,4-hydroxyl-2-methoxy,4-hydroxyl-3-methoxy,4-hydroxyl-3,5-dimethoxy, trihydroxyl, 4-hydroxyl-3-ethoxy, or 4-hydroxyl-3,5-dimethoxy; w is selected from CH or N; and z is selected from CH or N.
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Paragraph 0039-0043

(2020/12/30)

Synthesis, antifungal and antibacterial activity of calix[4]arene-based 1,3,4-oxadiazole derivatives
We describe the synthesis of some novel p-tert-butylcalix[4]arene-based (5-aryl-1,3,4-oxadiazol-2-yl)2-chloroethanethioate derivatives (4a–e). These compounds were synthesized by the reaction of tetra-tert-butyl calix[4]arene (1) with (5-aryl-1,3,4-oxadiazol-2-yl)2-chloroethanethioate (3a–e) in the presence of potassium carbonate as a weak base and dry acetone as the solvent. All the newly synthesized calix[4]arene derivatives were characterized by elemental analysis and various spectroscopic methods such as FT-IR, 1H NMR,13C NMR, DEPT, and ESI-MS. The synthesized compounds were tested in vitro for their antibacterial and antifungal activities against Escherichia coli and Aspergillus fumigates in comparison with enrofloxacin and amphotericin as reference drugs, which are normally used for treating such infections. The synthesized compounds showed different inhibition zones against the tested bacteria and fungi. Compound 4c was found to be most effective against A. fumigates, whereas compound 4e was found to be equally effective against E. coli and A. fumigates.
Dono Gezelbash, Zahra,Akbari Dilmaghani, Karim
p. 1446 - 1452
(2020/03/11)

AMINO ACID DERIVATIVES FOR THE TREATMENT OF INFLAMMATORY DISEASES
The present disclosure provides certain amino acid derivatives that inhibit NF-kB activation and are therefore useful for the treatment of inflammatory diseases. Also provided are pharmaceutical compositions containing such compounds and processes for preparing such compounds.
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Page/Page column 64

(2020/08/13)

Efficient and Recyclable RuCl3 ? 3H2O Catalyst Modified with Ionic Diphosphine for the Alkoxycarbonylation of Aryl Halides
A series of ionic (mono-/di-)phosphines (L2, L4, and L6) with structural similarity and their corresponding neutral counterparts (L1, L3, and L5) were applied to modulate the catalytic performance of RuCl3 ? 3H2O. With the involvement of the ionic diphosphine (L4), in which the two phosphino-fragments were linked by butylene group, RuCl3 ? 3H2O with advantages of low cost, robustness, and good availability was found to be an efficient and recyclable catalyst for the alkoxycarbonylation of aryl halides. The L4-based RuCl3 ? 3H2O system corresponded to the best conversion of PhI (96 %) along with 99 % selectivity to the target product of methyl benzoate as well as the good generality to alkoxycarbonylation of different aryl halides (ArX, X=I and Br) with alcohols MeOH, EtOH, i-PrOH and n-BuOH. The electronic and steric effects of the applied phosphines, which were analyzed by the 31P NMR for 1J31P-77Se1J measurement and single-crystal X-ray diffraction, were carefully co-related to the performance RuCl3 ? 3H2O catalyst. In addition, the L4-based RuCl3 ? 3H2O system could be recycled successfully for at least eight runs in the ionic liquid [Bmim]PF6.
Zhou, Qing,Liu, Lei,Guo, Wen-Di,Liang, Wen-Yu,Lu, Yong,Liu, Ye
p. 166 - 172
(2019/02/01)

Pd-Colloids-Catalyzed/Ag2O-Oxidized General and Selective Esterification of Benzylic Alcohols
Palladium colloids obtained from the degradation of Hermann–Beller palladacycle proved to be an efficient catalytic system in combination with silver oxide as a selective oxidant for the oxidative esterification of differently substituted benzyl alcohols in MeOH as solvent. Excellent reactivity exhibited by the catalytic system also allowed the alcoholic coupling partner to be changed from MeOH to a wide range of alcohols having diverse functionalities. The mildness of the developed protocol also made it possible to employ propargyl alcohol as the coupling partner without any observation of any interference of the terminal alkyne. Selective oxidative coupling of a primary alcoholic functional group over secondary in the case of glycols and glycerols was also made possible using the developed catalyst system. To test the relevancy of Pd/Ag combined catalysis mixed Pd/Ag colloids were synthesized, characterized by TEM, XRD and XPS and applied to oxidative-esterification successfully.
Sable, Vaibhav,Shah, Jagrut,Sharma, Anuja,Kapdi, Anant R.
supporting information
p. 2639 - 2647
(2019/07/08)

Camphoryl imidazole type ionic liquid and preparation method and application thereof
The invention discloses a camphoryl imidazole type ionic liquid and a preparation method and application thereof. According to the preparation method, a derivative camphorsulfonic acid of a natural renewable resource camphor is taken as a raw material to prepare 10-iodocamphor; then the 10-iodocamphor and aryl imidazole are subjected to a quaterisation reaction to prepare camphoryl imidazole iodide; then the camphoryl imidazole iodide and sodium hexafluorophosphate, sodium tetrafluoroborate, bis(trifluorosulfonimide)lithium and the like are subjected to ion exchange to prepare camphoryl imidazole hexafluorophosphate, camphoryl imidazole tetrafluoroborate, camphoryl imidazole bis(trifluorosulfonimide)salt and other ionic liquids. The camphoryl imidazole type ionic liquid shows good catalytic activity for an oxidation esterification reaction of aldehyde-alcohol, has the advantages of short reaction time, good reaction selectivity and high product yield, and has a good application prospect.
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Paragraph 0060; 0063

(2019/10/05)

METHOD FOR THE SYNTHESIS AND PURIFICATION OF ARYL ACID ESTERS
The general inventive concepts are directed to the discovery that certain aryl acids can be esterified under particular conditions to provide the resulting ester as a solid that precipitates in good yield from the reaction mixture. The esters may then be isolated and purified with relative ease. Accordingly, a method for the esterification, isolation, and purification of aryl acids is provided.
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Paragraph 0029-0030

(2019/10/17)

1,3-Dibromo-5,5-dimethylhydantoin as a Precatalyst for Activation of Carbonyl Functionality
Activation of carbonyl moiety is one of the most rudimentary approaches in organic synthesis and is crucial for a plethora of industrial-scale condensation reactions. In esterification and aldol condensation, which represent two of the most important reactions, the susceptibility of the carbonyl group to nucleophile attack allows the construction of a variety of useful organic compounds. In this context, there is a constant need for development of and improvement in the methods for addition-elimination reactions via activation of carbonyl functionality. In this paper, an advanced methodology for the direct esterification of carboxylic acids and alcohols, and for aldol condensation of aldehydes using widely available, inexpensive, and metal-free 1,3-dibromo-5,5-dimethylhydantoin under neat reaction conditions is reported. The method is air- and moisture-tolerant, allowing simple synthetic and isolation procedures for both reactions presented in this paper. The reaction pathway for esterification is proposed and a scale-up of certain industrially important derivatives is performed.
?ebular, Klara,Bo?i?, Bojan ?.,Stavber, Stojan
supporting information

(2019/08/01)

Synthesis, characterization, and nonlinear optical properties of some new series of S-(5-aryl-1,3,4-oxadiazol-2-yl) 2-chloroethanethioate derivatives
In the present investigation, some novel S-(5-aryl-1,3,4-oxadiazol-2-yl)2-chloroethanethioate (3a–3e) derivatives were synthesized and their impact on optical properties was studied. They have also been characterized by elemental analysis and various spectroscopic methods including FTIR, 1 H NMR, 13 C NMR, and UV-Vis techniques. The nonlinear refractive indexes of 3a–3e were also measured in dichloromethane via Z-scan method using a continuous wave diode-pumped laser at 532 nm wavelength. The nonlinear refractive coefficient of compounds was obtained from 1011 m2/W order. Regarding the appropriate nonlinearity of these compounds, they could be considered good candidates for biooptical and photonic applications. All the synthesized compounds (3a–3e) have also been evaluated for their antimicrobial and antifungal activities. The bioactive assay showed that the synthetic compounds displayed variable inhibition zones against tested bacterium Escherichia coli and fungus Aspergillus fumigatus in comparison to enrofloxacin and amphotericin as reference drugs, which are normally used for treating such infections.
Ghezelbash, Zahra Dono,Motiei, Hamideh,Mahmoody, Miri,Dilmaghani, Karim Akbari
p. 902 - 910
(2019/07/17)

Formation of esters and amides via metal-free Csp2-Csp3 bond cleavage of α-nitro ketone: Mechanistic insight to the reaction pathway
A catalyst free protocol for hucleophilic Csp2-Csp3 bond cleavage of a-nitroketone has been achieved for the formation of C-O and C-N bond. A series of differently substituted a-nitroketones could be selectively cleaved and converted into corresponding esters and tosylamides in presence of alcohols and bromamine-T respectively. Mechanism of the C-C bond cleavage has been proposed by identifying different reaction intermediates using IR and NMR spectroscopic methods.
Sarma, Manas Jyoti,Phukan, Prodeep
p. 523 - 533
(2019/05/21)

Phosphite-catalyzed alkoxycarbonylation of aryl diazonium salts
In this communication, an interesting phosphite-catalyzed alkoxycarbonylation of aryl diazonium salts has been reported. At room temperature and under CO pressure, moderate to good yields of the desired esters can be produced in the absence of bases or an
Xu, Jian-Xing,Franke, Robert,Wu, Xiao-Feng
supporting information
p. 6180 - 6182
(2018/09/10)

Study of new synthesized ferrocenyl ionic liquids in oxidative esterification reaction
In this work, novel ferrocene-based ionic liquids, 1-(ferrocenylbutyl)-4-(3-methylimidazolium) Azide and 1-(ferrocenylbutyl)-4-(3-methylimidazolium) Tetrafluoroborate, were synthesized and utilized in the oxidation esterification reaction of aldehydes in the present of different reagents such as NaN3, (K2CO3 and NCS), (KI and KCN), (I2 and K2CO3), (KMnO4). The results were compared with that of [BMIM][X] (X?Cl, BF4) under the same conditions. As expected, ferrocene-based ionic liquids showed better results; It seems, iron nuclear may play a similar role such as iron catalysts in these novel ionic liquids and can facilitated the oxidation esterification reaction with improve the yield and decrease the reaction time.
Teimuri-Mofrad, Reza,Rahimpour, Keshvar,Rezaei, Hannaneh,Valizadeh, Hassan,Aghaiepour, Alireza
p. 1425 - 1435
(2018/04/05)

Synthesis, characterization and catalytic performances of benzimidazolin-2-iminato actinide (IV) complexes in the Tishchenko reactions for symmetrical and unsymmetrical esters
A new family of benzimdazolin-2-iminato actinide?(IV) complexes [(Bim7-MeDipp/MeN)An(N(SiMe3)2)3] (An = U (3), Th (4)) and [(Bim4-MeDipp/MeN)An(N(SiMe3)2)3] (An = U (5), Th (6)) were synthesized and their solid state structures were established by single-crystal X-ray diffraction analysis. The catalytic performances of complexes 3–6 towards the homo- and cross-coupling of aldehydes (Tishchenko reaction) were studied and the thorium complexes 4 and 6 displayed moderate to high activities for the production of the corresponding symmetric and unsymmetrical esters. Coupling of aldehyde and alcohols, known as the tandem proton-transfer esterification, and the intermolecular coupling reaction between aldehyde and trifluoromethylketones were also investigated by these thorium complexes, indicating a complementary method to obtain unsymmetrical esters selectively. Plausible mechanisms for these reactions are proposed based on stoichiometric studies.
Liu, Heng,Khononov, Maxim,Fridman, Natalia,Tamm, Matthias,Eisen, Moris S.
p. 123 - 137
(2017/10/25)

Acylhydrazone compounds with anti-tumor activity as well as preparation method and application of acylhydrazone compounds
The invention belongs to the technical field of medicinal chemistry, and in particular relates to acylhydrazone compounds with anti-tumor activity as well as a preparation method and application of the acylhydrazone compounds. The structures of the acylhydrazone compounds are as shown in a general formula (I) shown in the description, wherein R and R' are independently selected from any one or more of halogen, amino, cyano, alkoxy, 3,4-methylenedioxy, nitro, phenyl or substituted phenyl, and R and R' substituents are mono-substituted, disubstituted or tri-substituted. The preparation method issimple; biological activity test results of the compounds show that the compounds have a very good inhibitory effect on histone methyltransferase SET7, and have good application prospect in the development of anti-tumor aspects.
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Paragraph 0043; 0044; 0045; 0046

(2018/05/16)

Efficient synthesis of esters through oxone-catalyzed dehydrogenation of carboxylic acids and alcohols
Since esters are important organic synthesis intermediates, an environmentally friendly oxone catalyzed-esterification of carboxylic acids with alcohols has been developed. A series of carboxylic acid esters are obtained in high yield. This strategy requires mild reaction conditions, providing an attractive alternative for the construction of valuable carbonyl esters. Electron-rich and electron-deficient groups are compatible with the standard conditions and a variety of substrates are demonstrated. Moreover, the reaction could easily be adapted to typical prodrugs, drugs and gram-scale synthesis.
Hou, Fei,Wang, Xi-Cun,Quan, Zheng-Jun
supporting information
p. 9472 - 9476
(2019/01/03)

Esterification of aryl/alkyl acids catalysed by n-bromosuccinimide under mild reaction conditions
N-halosuccinimides (NXSs) are well-known to be convenient, easily manipulable and low-priced halogenation reagents in organic synthesis. In the present work, N-bromosuccinimide (NBS) has been promoted as the most efficient and selective catalyst among the NXSs in the reaction of direct esterification of aryl and alkyl carboxylic acids. Comprehensive esterification of substituted benzoic acids, mono-, di- and tri-carboxy alkyl derivatives has been performed under neat reaction conditions. The method is metal-free, air- and moisture-tolerant, allowing for a simple synthetic and isolation procedure as well as the large-scale synthesis of aromatic and alkyl esters with yields up to 100%. Protocol for the recycling of the catalyst has been proposed.
?ebular, Klara,Bo?i?, Bojan ?.,Stavber, Stojan
(2018/09/10)

A scalable and safe continuous flow procedure for in-line generation of diazomethane and its precursor MNU
Diazomethane is a valuable C1-building block for organic synthesis. Due to its intrinsic reactivity and instability, handling of this reagent is associated with serious safety hazards. Herein we present a simple and robust continuous flow process, allowing a safe and on-demand generation of diazomethane with a productivity of 95-117 mmol h-1. The developed two-step process starts from non-hazardous N-methylurea, and generates and consumes N-methyl-N-nitrosourea (MNU) and diazomethane, thus enabling a safe and convenient scale-up to a multi-gram scale in a conventional synthesis laboratory.
Lehmann
supporting information
p. 1449 - 1453
(2017/05/10)

Oxalic acid as the: In situ carbon monoxide generator in palladium-catalyzed hydroxycarbonylation of arylhalides
An efficient palladium-catalyzed hydroxycarbonylation reaction of arylhalides using oxalic acid as a CO source has been developed. The reaction features high safety, low catalyst loading, and a broad substrate scope, and provides a safe and tractable approach to access a variety of aromatic carboxylic acid compounds. Mechanistic studies revealed the decomposition pattern of oxalic acid.
Shao, Changdong,Lu, Ailan,Wang, Xiaoling,Zhou, Bo,Guan, Xiaohong,Zhang, Yanghui
supporting information
p. 5033 - 5040
(2017/07/10)

The dinitro compound production
PROBLEM TO BE SOLVED: To provide a method of producing a high-purity dinitro compound to be a raw material of poly(imide-benzoxazole) from diaminophenol and nitrobenzoyl chloride by a simple method.SOLUTION: Illustrated is a method of producing a dinitro compound represented by the following formula by making, for example, 3-nitrobenzoyl chloride and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane react with each other in nitrogen-containing organic solvent.
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Paragraph 0088

(2018/01/11)

Convenient, metal-free ipso-nitration of arylboronic acids using nitric acid and trifluoroacetic acid
A feasible protocol for the direct ipso-nitration of arylboronic acids using trifluoroacetic acid and nitric acid as nitration reagent has been developed. Various aromatic nitro compounds are produced in moderate to good yields under the metal-free conditions. The method is operationally simple and regioselective, and might have potential application in industry.
Shen, Guodong,Zhao, Lingyu,Liu, Wanxing,Huang, Xianqiang,Song, Huina,Zhang, Tongxin
supporting information
p. 10 - 14
(2016/12/30)

Efficient and selective palladium-catalyzed direct oxidative esterification of benzylic alcohols under aerobic conditions
A highly efficient palladium-catalyzed approach for the direct oxidative esterification of benzylic alcohols with methanol and long-chain aliphatic alcohols under mild conditions has been achieved. This practical catalyst system exhibits a broad substrate scope and good functional group tolerance. Catalytic amount of Bi(OTf)3 is used as co-catalyst to improve the activity and selectivity of the reactions. A variety of esters are obtained in yields of 43–96%.
Hu, Yongke,Li, Bindong
p. 7301 - 7307
(2017/11/29)

Amberlyst-15 catalysed oxidative esterification of aldehydes using a H2O2 trapped oxidant as a terminal oxidant
A simple and efficient method has been developed for the selective oxidative esterification of aldehydes using commercially available Amberlyst-15 as a catalyst. H2O2 released from a clathrate structured 4Na2SO4·2H2O2·NaCl oxidant serves as an efficient source of terminal oxidants. Various aromatic, heteroaromatic, and aliphatic aldehydes undergo selective esterification to give good to excellent yield. The heterogeneous catalyst, Amberlyst-15, exhibits high reactivity and can be recycled over several runs. The 4Na2SO4·2H2O2·NaCl oxidant was found to be superior to commonly used oxidizing agents providing an anhydrous, easy to handle and stable form of H2O2
Gayakwad, Eknath M.,Patil, Vilas V.,Shankarling, Ganapati S.
p. 2695 - 2701
(2017/04/03)

Solvent- and Metal-free Oxidative Esterification of Aromatic Aldehydes Using Urea-2,2-dihydroperoxypropane as a New Solid Oxidant
Urea-2,2-dihydroperoxypropane as a noble and solid gem-dihydroperoxide derivative was used to transform various aromatic aldehydes to their corresponding benzoate derivatives in the presence of HBr under mild conditions at room temperature in high yields and short reaction times.
Khosravi, Kaveh,Khalaji, Kobra,Naserifar, Shirin
p. 303 - 309
(2017/03/27)

Facile Coupling of Aldehydes with Alcohols: An Evolved Tishchenko Process for the Preparation of Unsymmetrical Esters
A facile coupling process between aldehydes and alcohols to afford unsymmetrical esters is presented herein. This transformation is complementary to the Tishchenko reaction and provides access to unsymmetrical esters under very mild conditions. Various aldehydes and alcohols are suitable in this reaction, and the addition of a sacrificial trifluoromethyl ketone allows the process to take place in a highly selective manner. A plausible mechanism based on details obtained by monitoring the reaction progress and deuterium-labeling studies has been proposed.
Liu, Heng,Eisen, Moris S.
p. 4852 - 4858
(2017/09/07)

Selective Actinide-Catalyzed Tandem Proton-Transfer Esterification of Aldehydes with Alcohols for the Production of Asymmetric Esters
Actinide-catalyzed tandem proton-transfer esterification between aldehydes and alcohols is presented herein for the first time. It represents a novel convenient and external-oxidant-free methodology in the preparation of asymmetric ester compounds. Various kinds of aldehydes and alcohols can be applied to this reaction, affording the corresponding ester product in moderate to high yields. A plausible mechanism was proposed on the basis of the kinetic, stoichiometric, and deuterium-labeling studies.
Liu, Heng,Eisen, Moris S.
supporting information
p. 1461 - 1464
(2017/04/28)

Fe-Catalyzed Aerobic Oxidative C-CN Bond Cleavage of Arylacetonitriles Leading to Various Esters
Fe-catalyzed aerobic oxidative esterifications of arylacetonitriles with alcohols, tri alkoxsilanes, silicate esters, or borate esters have been developed. The acyl groups which were in situ generated via chemoselective C(CO)-CN bond cleavage were directly used as electrophiles, leading to corresponding aryl esters in good to excellent yields under molecular oxygen when attacked by alcohols or alcohol surrogates. Dioxygen serves as both oxidant and reactant in this protocol. The reaction has a very broad substrate scope. Cheap starting materials as well as environmentally benign and inexpensive iron catalyst and ideal oxidant O2 feature this transformation and make it a practical and sustainable protocol to afford esters.
Kong, Weiguang,Li, Bingnan,Xu, Xuezhao,Song, Qiuling
p. 8436 - 8443
(2016/09/28)

Oxidative Esterification of Aromatic Aldehydes Using Polymer-Supported Green Bromine
A facile one-pot green chemical conversion of aromatic aldehydes to alkyl esters is described using polymer-supported bromine chloride resin in the presence of potassium carbonate at room temperature. This eco-friendly methodology with simple workup procedure and recovery and recyclability of the resin makes the transformation simple and efficient.
Sridhar,Swarnalakshmi,Selvaraj
p. 1344 - 1348
(2016/06/01)

Chemoselective dehydrogenative esterification of aldehydes and alcohols with a dimeric rhodium(II) catalyst
Dehydrogenative cross-coupling of aldehydes with alcohols as well as dehydrogentive cross-coupling of primary alcohols to produce esters have been developed using a Rh-terpyridine catalyst. The catalyst demonstrates broad substrate scope and good functional group tolerance, affording esters highly selectively. The high chemoselectivity of the catalyst stems from its preference for dehydrogenation of benzylic alcohols over aliphatic ones. Preliminary mechanistic studies suggest that the active catalyst is a dimeric Rh(ii) species, operating via a mechanism involving metal-base-metal cooperativity.
Cheng, Junjie,Zhu, Meijuan,Wang, Chao,Li, Junjun,Jiang, Xue,Wei, Yawen,Tang, Weijun,Xue, Dong,Xiao, Jianliang
p. 4428 - 4434
(2016/07/07)

NOVEL SINGLE STEP ESTERIFICATION PROCESS OF ALDEHYDES USING A HETEROGENEOUS CATALYST
The present invention relates to a novel simple, efficient and single-step process for esterification of aldehydes using a heterogeneous catalyst with high yields. More particularly, the present invention relates to a novel simple, efficient and single-step process for esterification of aldehydes using Titanium superoxide with greater than 80% yields.
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(2016/06/20)

N-Doped Sub-3 nm Co Nanoparticles as Highly Efficient and Durable Aerobic Oxidative Coupling Catalysts
A nano-coating associated with sulfuric acid leaching protocol was developed to prepare N-doped sub-3 nm Co-based nanoparticle catalyst (Co?N/C) using melamine–formaldehyde resin as the N-containing precursor, active carbon as the support, and Co(NO3)2 as the Co-containing precursor. By thermal treatment under nitrogen atmosphere at 800 °C and leached with sulfuric acid solution, a stable and highly dispersive Co?N coordination structure was uniformly dispersed on the formed Co?N/C catalyst with a Co loading of 0.47 wt % and Co nanoparticle size of 2.55 nm. The Co?N/C catalyst was characterized with XRD, XPS, Raman, SEM, TEM, ICP, and elemental analysis. The Co?N/C catalyst showed extremely high catalytic efficiency with a TON of 257 for the aerobic oxidative coupling of aldehydes with methanol to directly synthesize methyl esters with molecular oxygen as the final oxidant. The Co?N/C catalyst also showed broad substrate range and stable recyclability. After recycling for 7 times, no obvious deactivation was detected. It was confirmed that the sub-3 nm Co?N coordination structure formed between metallic Co nanoparticles and pyridinic nitrogen doping into graphitic layers functions as the active site to activate molecular oxygen for the β-H elimination from generated hemiacetal intermediates to produce methyl esters. The nano-coating associated with acid leaching protocol provides a novel strategy to prepare highly efficient non-precious metal-based catalysts.
Han, Junxing,Gu, Feifei,Li, Yuchao
p. 2594 - 2601
(2016/09/28)

DEHYDRATION CONDENSATION AGENT
PROBLEM TO BE SOLVED: To provide a novel compound useful as a dehydration condensation agent. SOLUTION: This invention relates to a compound represented by formula (I) [where each symbol is as defined in the specifications] and to a method for producing a carboxylic acid derivative (ester, amide or the like) that uses the compound as a dehydration condensation agent. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0355

(2018/09/08)

Design and Synthesis of Janus Kinase 2 (JAK2) and Histone Deacetlyase (HDAC) Bispecific Inhibitors Based on Pacritinib and Evidence of Dual Pathway Inhibition in Hematological Cell Lines
Blockage of more than one oncoprotein or pathway is now a standard approach in modern cancer therapy. Multiple inhibition is typically achieved with two or more drugs. Herein, we describe a pharmacophore merging strategy combining the JAK2/FLT3 inhibitor pacritnib with the pan-HDAC inhibitor, vorinostat, to create bispecific single molecules with both JAK and HDAC targeted inhibition. A preferred ether hydroxamate, 51, inhibits JAK2 and HDAC6 with low nanomolar potency, is 50-fold selective for JAK2 in a panel of 97 kinases. Broad cellular antiproliferative potency is supported by demonstration of JAK-STAT and HDAC pathway blockade in several hematological cell lines, inhibition of colony formation in HEL cells, and analysis of apoptosis. This study provides new tool compounds for further exploration of dual JAK-HDAC pathway inhibiton achieved with a single molecule.
Yang, Eugene Guorong,Mustafa, Nurulhuda,Tan, Eng Chong,Poulsen, Anders,Ramanujulu, Pondy Murugappan,Chng, Wee Joo,Yen, Jeffrey J. Y.,Dymock, Brian W.
supporting information
p. 8233 - 8262
(2016/10/03)

Indole ketone compound or its derivatives and their use
The present invention relates to indolone compounds shown by general formula (a) or derivatives thereof, and uses thereof. The technical problem solved by the present invention is to provide indolone compounds or derivatives thereof, and uses thereof. The present invention uses a deuterium-enriched indolone compound obtained from a deuterium-substituted indolone compound. The above-mentioned indolone compounds can simultaneously effect on three key receptor families involved in the process of blood vessel formation, i.e., vascular endothelial growth factor receptor (VEGFR), fibroblast growth factor receptor (FGFR), and platelet-derived growth factor receptor (PDGFR), and inhibit the formation of blood vessel, thereby achieving the effect of treating cancers. The above-mentioned deuterium-substituted indolone compounds or derivatives thereof have the advantage of high efficiency as medicaments.
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Paragraph 0161; 0163; 0164; 0165

(2017/02/02)

Antiurease, antiphosphodiesterase and antiglycation studies of Pd(II) complexes with monodentate hydrazides
The present study was aimed to synthesize and characterize a series of Pd(II)-benzohydrazide complexes with subsequent high throughput screening to seek their effects as enzyme inhibitors and antiglycating agents. Based on complete characterization via elemental (CHN, Pd) analysis, physical (conductivity, magnetic moment) measurements and spectral (FT-IR, 1H-NMR, 13C-NMR) techniques, all Pd(II) complexes were identified as diamagnetic, neutral and orienting in trans square planar geometry with general formula [PdL2Cl2]. The benzohydrazide (L) in these complexes depicts monodentate behavior, providing terminal amino nitrogen as a donor atom. Compared to inactive precursors (free benzohydrazides and Pd2+), almost all Pd(II) complexes showed in vitro antiglycation activity, illustrating the potential role of resulting complexes in the suppression of diabetes and related disorders. The presence of free carbonyl group in complexes has been recognized as possible cause of antiglycation. This study also indicated Pd(II) compounds as far more superior inhibitors of urease and phosphodiesterase-I than parent ligands; many of them exhibited inhibitions equivalent or even greater than the standard inhibitors (thiourea, urease; EDTA, phosphodiesterase), which shows their potential use in future in the control of peptic ulcer and arthritis, respectively. The structure activity relationship (SAR) study demonstrated that complexation, steric hindrance, position of substituents, electron density around metal centre, hydrogen bonding and coordination mode of complexed ligands play prime role in modulating the biological activities of complexes.
Qurrat-Ul-Ain,Rasheed, Saima,Mahroof-Tahir, Mohammad,Ashiq, Uzma,Jamal, Rifat Ara,Khurshid, Sumaira,Mustafa, Sana
p. 864 - 881
(2016/11/21)

Rhodium-Catalyzed Double Alkyl-Oxygen Bond Cleavage: An Alkyl Transfer Reaction from Bis/Tris(o-alkyloxyphenyl)phosphine to Aryl Acids
An unprecedented rhodium-catalyzed selective cleavage of double alkyl-oxygen bonds of bis/tris(o-alkyloxyphenyl)phosphine has been realized, in which P atom functions as a directing group and simple aryl acids are the methyl group acceptor to provide methyl esters and a quaternary phosphonium salt. The preliminary mechanism was investigated via an 18O labeling experiment and stoichiometric reaction between a Rh-A crystal and an aromatic acid.
Zhou, Hui,Zhang, Jinlong,Yang, Huameng,Xia, Chungu,Jiang, Gaoxi
supporting information
p. 3406 - 3412
(2016/10/21)

Copper(II)-directed static excimer formation of an anthracene-based highly selective fluorescent receptor
A novel 'turn-on' fluorescent receptor methyl 3-((anthracen-9-ylmethylene)amino)benzoate (MAB) with anthracene as the fluorophore and methyl 3-aminobenzoate as a metal ion chelating center has been designed and synthesized. The ability of the prepared receptor to detect metal ions has been evaluated by the changes in its emission intensity. MAB demonstrates high selectivity and sensitivity for Cu2+ among the nineteen metal ions examined in MeCN. The interaction of MAB with Cu2+ causes a significant enhancement in emission intensity due to the combination of a unique anthracenyl static excimer formation, the restricted CN isomerization and the suppression of highly efficient photoinduced electron transfer (PET) process. The disassociation of the excimer species to monomers is directed by temperature, Cu2+ concentration and solvent fraction. Furthermore, the considerable 'off-on' fluorescence response or the conversion of the excimer species to monomers concomitantly led to the apparent color changes, which could also be identified easily by the naked eye using a UV lamp.
Malkondu, Sait,Turhan, Dilek,Kocak, Ahmet
p. 162 - 167
(2015/02/18)

Efficient and practical approach to esters from acids/ 2-oxoacids/ 2-oxoaldehydes &/ 2-oxoesters
An efficient, mild, cost effective and practical method is presented for generation of esters (RCO2R′) from acids (RCO2H)/ 2-oxoacids (RCOCO2H)/ 2-oxoaldehydes (RCOCHO)/ 2-oxoesters (RCOCO2R″) and alcohols by using oxone as catalyst. In addition to deciphering the scope of our process, we propose a mechanism for esterification through a common intermediate IV. Reaction with 2-oxoacids and 2-oxoaldehydes proceed with initial CO-C cleavage followed by oxone mediated esterification with alcohols. In addition, reaction with 2-oxoesters proceeds through CO-CO bond cleavage and trans-esterification.
Padala, Anil K.,Saikam, Varma,Ali, Asif,Ahmed, Qazi Naveed
supporting information
p. 9388 - 9395
(2015/11/18)