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Broadening antifungal spectrum and improving metabolic stablity based on a scaffold strategy: Design, synthesis, and evaluation of novel 4-phenyl-4,5-dihydrooxazole derivatives as potent fungistatic and fungicidal reagents
5-phenylthiophene derivatives exhibited excellent antifungal activity against Candida albicans, Candida tropicalis and Cryptococcus neoformans. However, optimal compound 7 was inactive against Aspergillus fumigatus and unstable in human liver microsomes in vitro with a half-life of 18.6 min. To discover antifungal agents with a broad spectrum and improve the metabolic properties of the compounds, the scaffold hopping strategy was adopted and a series of 4-phenyl-4,5-dihydrooxazole derivatives were designed and synthesized. It was especially encouraging that compound 22a displayed significant antifungal activities against eight susceptible strains and seven FLC-resistant strains. Furthermore, the potent compound 22a could prevent the formation of fungalbiofilms and displayed satisfactory fungicidal activity. In addition, the metabolic stability of compound 22a was improved significantly, with the half-life of 70.5 min. Compound 22a was almost nontoxic to mammalian A549, MCF-7, HepG2, and 293T cells. Moreover, pharmacokinetic studies in SD rats showed that compound 22a exhibited pharmacokinetic properties with a bioavailability of 15.22% and a half-life of 4.44 h, indicating that compound 22a is worthy of further study.
Cheng, Maosheng,Cui, Hengxian,Jiang, Hong,Liu, Lei,Su, Xin,Sun, Yin,Wu, Tianxiao,Yin, Wenbo,Zhang, Yuxin,Zhao, Dongmei,Zhao, Liyu
(2021/11/11)

Design, synthesis, and biological activity evaluation of 2-(benzo[b]thiophen-2-yl)-4-phenyl-4,5-dihydrooxazole derivatives as broad-spectrum antifungal agents
To discover antifungal compounds with broad-spectrum and stable metabolism, a series of 2-(benzo[b]thiophen-2-yl)-4-phenyl-4,5-dihydrooxazole derivatives was designed and synthesized. Compounds A30-A34 exhibited excellent broad-spectrum antifungal activity against Candida albicans with MIC values in the range of 0.03–0.5 μg/mL, and against Cryptococcus neoformans and Aspergillus fumigatus with MIC values in the range of 0.25–2 μg/mL. In addition, compounds A31 and A33 showed high metabolic stability in human liver microsomes in vitro, with the half-life of 80.5 min and 69.4 min, respectively. Moreover, compounds A31 and A33 showed weak or almost no inhibitory effect on the CYP3A4 and CYP2D6. The pharmacokinetic evaluation in SD rats showed that compound A31 had suitable pharmacokinetic properties and was worthy of further study.
Zhao, Liyu,Sun, Yin,Yin, Wenbo,Tian, Linfeng,Sun, Nannan,Zheng, Yang,Zhang, Chu,Zhao, Shizhen,Su, Xin,Zhao, Dongmei,Cheng, Maosheng
(2021/11/22)

Nickel-Catalyzed NO Group Transfer Coupled with NOxConversion
Nitrogen oxide (NOx) conversion is an important process for balancing the global nitrogen cycle. Distinct from the biological NOx transformation, we have devised a synthetic approach to this issue by utilizing a bifunctional metal catalyst for producing value-added products from NOx. Here, we present a novel catalysis based on a Ni pincer system, effectively converting Ni-NOx to Ni-NO via deoxygenation with CO(g). This is followed by transfer of the in situ generated nitroso group to organic substrates, which favorably occurs at the flattened Ni(I)-NO site via its nucleophilic reaction. Successful catalytic production of oximes from benzyl halides using NaNO2 is presented with a turnover number of >200 under mild conditions. In a key step of the catalysis, a nickel(I)-?NO species effectively activates alkyl halides, which is carefully evaluated by both experimental and theoretical methods. Our nickel catalyst effectively fulfills a dual purpose, namely, deoxygenating NOx anions and catalyzing C-N coupling.
Padmanaban, Sudakar,Choi, Jonghoon,Vazquez-Lima, Hugo,Ko, Donghwi,Yoo, Dagyum,Gwak, Jinseong,Cho, Kyung-Bin,Lee, Yunho
supporting information
p. 4585 - 4593
(2022/03/02)

Cyanide-Free Cyanation of Aryl Iodides with Nitromethane by Using an Amphiphilic Polymer-Supported Palladium Catalyst
A cyanide-free aromatic cyanation was developed that uses nitromethane as a cyanide source in water with an amphiphilic polystyrene poly(ethylene glycol) resin-supported palladium catalyst and an alkyl halide (1-iodobutane). The cyanation proceeds through the palladium-catalyzed cross-coupling of an aryl halide with nitromethane, followed by transformation of the resultant (nitromethyl)arene intermediate into a nitrile by 1-iodobutane.
Niimi, Ryoko,Suzuka, Toshimasa,Uozumi, Yasuhiro
supporting information
p. 40 - 44
(2021/11/30)

Integrating Hydrogen Production and Transfer Hydrogenation with Selenite Promoted Electrooxidation of α-Nitrotoluenes to E-Nitroethenes
Developing an electrochemical carbon-added reaction with accelerated kinetics to replace the low-value and sluggish oxygen evolution reaction (OER) is markedly significant to pure hydrogen production. Regulating the critical steps to precisely design electrode materials to selectively synthesize targeted compounds is highly desirable. Here, inspired by the surfaced adsorbed SeOx2? promoting OER, NiSe is demonstrated to be an efficient anode enabling α-nitrotoluene electrooxidation to E-nitroethene with up to 99 % E selectivity, 89 % Faradaic efficiency, and the reaction rate of 0.25 mmol cm?2 h?1 via inhibiting side reactions for energy-saving hydrogen generation. The high performance can be associated with its in situ formed NiOOH surface layer and absorbed SeOx2? via Se leaching-oxidation during electrooxidation, and the preferential adsorption of two -NO2 groups of intermediate on NiOOH. A self-coupling of α-carbon radicals and subsequent elimination of a nitrite molecule pathway is proposed. Wide substrate scope, scale-up synthesis of E-nitroethene, and paired productions of E-nitroethene and hydrogen or N-protected aminoarenes over a bifunctional NiSe electrode highlight the promising potential. Gold also displays a similar promoting effect for α-nitrotoluene transformation like SeOx2?, rationalizing the strategy of designing materials to suppress side reactions.
Chong, Xiaodan,Liu, Cuibo,Wang, Changhong,Yang, Rong,Zhang, Bin
supporting information
p. 22010 - 22016
(2021/09/02)

Improving the metabolic stability of antifungal compounds based on a scaffold hopping strategy: Design, synthesis, and structure-activity relationship studies of dihydrooxazole derivatives
L-amino alcohol derivatives exhibited high antifungal activity, but the metabolic stability of human liver microsomes in vitro was poor, and the half-life of optimal compound 5 was less than 5 min. To improve the metabolic properties of the compounds, the scaffold hopping strategy was adopted and a series of antifungal compounds with a dihydrooxazole scaffold was designed and synthesized. Compounds A33-A38 substituted with 4-phenyl group on dihydrooxazole ring exhibited excellent antifungal activities against C. albicans, C. tropicalis and C. krusei, with MIC values in the range of 0.03–0.25 μg/mL. In addition, the metabolic stability of compounds A33 and A34 in human liver microsomes in vitro was improved significantly, with the half-life greater than 145 min and the half-life of 59.1 min, respectively. Moreover, pharmacokinetic studies in SD rats showed that A33 exhibited favourable pharmacokinetic properties, with a bioavailability of 77.69%, and half-life (intravenous administration) of 9.35 h, indicating that A33 is worthy of further study.
Cheng, Maosheng,Su, Xin,Sun, Nannan,Sun, Yin,Tian, Linfeng,Yin, Wenbo,Zhang, Chu,Zhao, Dongmei,Zhao, Liyu,Zhao, Shizhen,Zheng, Yang
(2021/08/07)

Improved and Flexible Synthetic Access to the Spiroindole Backbone of Cebranopadol
By changing the dimethylamino to a nitro group, a novel synthetic access to the spirocyclic opioid analgesic cebranopadol was developed that is much more efficient compared with the established route. On the basis of the α-acidity of α-nitrotoluene, the two-fold Michael addition to acrylate gave an acyclic precursor compound, which was easily transformed by Dieckmann condensation and decarboxylation to the cyclohexanone derivative needed for the annulation of the indole ring by an oxa-Pictet-Spengler reaction. As an additional benefit, the reduction of the nitro group furnished an amine, which could be late-stage-diversified to carboxamides, sulfonamides, ureas, and N-alkyl congeners. The transformation of the nitro group at the spirocyclic scaffold to the dimethylamino function of the actual title compound was achieved in one step with zinc/formic acid/formaldehyde in 83% yield.
Christoffers, Jens,Schmidtmann, Marc,Wachtendorf, Daniel
supporting information
p. 6420 - 6423
(2020/09/02)

Transition-Metal-Free Three-Component Synthesis of Tertiary Aryl Amines from Nitro Compounds, Boronic Acids, and Trialkyl Phosphites
The synthesis of aromatic amines is of continuous interest in chemistry. An exceptionally versatile three-component reaction that directly transforms inexpensive nitro compounds, boronic acids, and trialkyl phosphites into tertiary aromatic amines has been realized. The reaction tolerates alkyl and aryl substituents on the nitro and boronic acid moieties, as well as functionalized phosphites. No transition-metal catalysis is required. The method is orthogonal to other classical metal-catalyzed syntheses since it tolerates the presence of halogens, and also permits the synthesis of functionalized compounds such as α-amino ester derivatives. (Figure presented.).
Roscales, Silvia,Csáky, Aurelio G.
supporting information
p. 111 - 117
(2019/11/16)

2, 4, 4-trisubstituted dihydrooxazole derivative and application thereof
The invention belongs to the technical field of drug synthesis, and relates to 2, 4, 4-trisubstituted dihydrooxazole derivatives, pharmaceutically acceptable salts, hydrates, solvates or prodrugs thereof, preparation methods of the 2, 4, 4-trisubstituted dihydrooxazole derivatives and the pharmaceutically acceptable salts, hydrates, solvates or prodrugs thereof, and an application of the 2, 4, 4-trisubstituted dihydrooxazole derivatives and the prodrugs thereof as drugs for treating various diseases caused by fungal infection. The general formula of the 2, 4, 4-trisubstituted dihydrooxazole derivative and the stereoisomer or the pharmaceutically acceptable salt, hydrate, solvate or prodrug thereof is shown as (I), wherein MBG, X, Y, M and R1 are shown in the claims and the specification. .
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Paragraph 0148-0150

(2020/11/12)

Unanticipated Silyl Transfer in Enantioselective α,β-Unsaturated Acyl Ammonium Catalysis Using Silyl Nitronates
The use of silyl nitronates is reported for the isothiourea-catalyzed synthesis of ?3-nitro-substituted silyl esters containing up to two contiguous stereocenters in good yields with excellent enantioselectivities (up to 93% yield and 99:1 er). The serendipitously discovered formation of silyl ester products in this reaction demonstrates a novel platform for catalyst turnover in α,β-unsaturated acyl ammonium catalysis.
Matviitsuk, Anastassia,Greenhalgh, Mark D.,Taylor, James E.,Nguyen, Xuan B.,Cordes, David B.,Slawin, Alexandra M. Z.,Lupton, David W.,Smith, Andrew D.
supporting information
p. 335 - 339
(2020/01/11)

Regioselective synthesis of 3,4-diaryl-5-unsubstituted isoxazoles, analogues of natural cytostatic combretastatin A4
4,5-Diarylisoxazoles are potent antiproliferative tubulin-targeting agents. Their isomeric 3,4-diaryl-5-unsubstituted isoxazoles are hardly accessible. The synthesis of 3,4-diaryl-5-unsubstituted isoxazoles 13 was designed based on a condensation of arylb
Chernysheva, Natalia B.,Maksimenko, Anna S.,Andreyanov, Fedor A.,Kislyi, Victor P.,Strelenko, Yuri A.,Khrustalev, Victor N.,Semenova, Marina N.,Semenov, Victor V.
supporting information
p. 511 - 518
(2018/02/15)

Green synthesis method for preparing nitroalkanes by oxime oxidation
The invention belongs to the field of organic chemical industries, and provides a green synthesis method for preparing nitroalkanes by oxime oxidation. At the temperature of 55 to 120 DEG C and under the pressure of 0 to 1.0 MPa, oxime, a solvent and hydrogen peroxide are reacted for 20 to 200min in the presence of certain amounts of nanoporous skeleton metal hybrid catalysts and cocatalysts, a reaction liquid is subjected to membrane separation, the catalysts can be repeatedly used for more than 7 times, and distilled to obtain nitroalkane products, the purity of the products is not less than 99%, and the yield of the products is not less than 95%. Furthermore, the green synthesis method for preparing nitroalkanes by the oxime oxidation disclosed by the invention is a green synthesis method of nitroalkanes, and suitable for large-scale industrialized production.
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Paragraph 0063; 0064

(2017/08/29)

Synthesis of 3,4-diaryl-5-carboxy-4,5-dihydroisoxazole 2-oxides as valuable synthons for anticancer molecules
The convenient regioselective scalable synthesis of 3,4-diaryl-5-carboxy-4,5-dihydroisoxazole 2-oxides was developed based on a condensation of simple starting materials (arylbenzaldehydes, arylnitromethanes, and ethoxycarbonylmethylpyridinium bromide) un
Chernysheva, Natalia B.,Maksimenko, Anna S.,Andreyanov, Fedor A.,Kislyi, Victor P.,Strelenko, Yuri A.,Khrustalev, Victor N.,Semenova, Marina N.,Semenov, Victor V.
p. 6728 - 6735
(2017/10/25)

Catalytic Asymmetric Cycloadditions of Silyl Nitronates Bearing α-Aryl Group
1,3-Dipolar cycloadditions of 2-alkylacroleins or atropaldehyde with triisopropylsilyl nitronates bearing an α-aryl group produced 3-aryl-2-isoxazolines having a chiral quaternary center in up to 94% ee and up to 88% yield with the aid of Corey’s oxazaborolidine catalyst. Specifically, the TIPS nitronate with an α-(p-methoxyphenyl) group gave mainly the 2-isoxazolines having an all-carbon quaternary center.
Jiang, Minghui,Feng, Lifei,Feng, Juanjuan,Jiao, Peng
supporting information
p. 2210 - 2213
(2017/05/12)

Conversion of nitroalkanes into carboxylic acids via iodide catalysis in water
We report a new method for the conversion of nitroalkanes into carboxylic acids that achieves this transformation under very mild conditions. Catalytic amounts of iodide in combination with a simple zinc catalyst are needed to give good conversions into the corresponding carboxylic acids.
Marcé, Patricia,Lynch, James,Blacker, A. John,Williams, Jonathan M. J.
supporting information
p. 1013 - 1016
(2016/01/16)

Scalable, easy synthesis, and efficient isolation of arylnitromethanes: a revival of the Victor Meyer reaction
A modified approach to synthesize and isolate arylnitromethanes is described. The method takes advantage of the significant difference in acidity between the arylnitromethane and the major impurity of the reaction, the nitrite ester. The arylnitromethanes resulting from this process are obtained in high yields and are analytically pure, i.e., they do not require distillation or further purification, which is a comfortable improvement of the ancestral Victor Meyer reaction.
Alaime, Thibaud,Delots, Audrey,Pasquinet, Eric,Suzenet, Franck,Guillaumet, Gérald
p. 1337 - 1341
(2017/01/21)

Catalytic enantioselective epoxidation of nitroalkenes
Nitroepoxides are potentially exploitable as synthons with vicinal electrophilic centers. Nevertheless, although advances have been made in the field, enantioselective epoxidation of nitroalkenes is still a challenging process. Herein we show a convenient procedure for the preparation of optically active nitroepoxides in high enantiomeric excess and high chemical yield. The kinetic data of the best catalyst have been examined using computational methods based on DFT calculations. Interestingly, the results demonstrate that the enantioselectivity of the epoxidation of nitroalkenes by this kind of catalyst is not only kinetically but also thermodynamically controlled.
Vidal-Albalat,?widerek,Izquierdo,Rodríguez,Moliner,González
supporting information
p. 10060 - 10063
(2016/08/15)

Organocatalytic enantioselective formal C(sp2)-H alkylation
An organocatalytic enantioselective formal C(sp2)-H alkylation is reported. This alkylative desymmetrization of prochiral 2,2-disubstituted cyclopentene-1,3-dione is catalyzed by a bifunctional tertiary aminourea derivative, utilizes air-stable and inexpensive nitroalkanes as the alkylating agents, and delivers synthetically versatile five-membered carbocycles containing an all-carbon quaternary stereogenic center remote from the reaction site in excellent enantioselectivity.
Manna, Madhu Sudan,Mukherjee, Santanu
supporting information
p. 130 - 133
(2015/01/30)

Palladium-Catalyzed Synthesis ofΔ2-Isoxazoline from Toluene Derivatives Enabled by the Triple Role of Silver Nitrate
A palladium-catalyzed direct synthesis ofΔ2-isoxazoline from toluene derivatives has been established. The present reaction proceeds through nondirected Csp3-H activation, benzylic nitration, dehydration, and cycloaddition. This protocol also features the unusual triple role of silver nitrate in a one-pot reaction.
Li, Chengliang,Deng, Hongmei,Li, Chunju,Jia, Xueshun,Li, Jian
supporting information
p. 5718 - 5721
(2015/12/01)

Asymmetric Michael addition of α-fluoro-α-nitroalkanes to nitroolefins: Facile preparation of fluorinated amines and tetrahydropyrimidines
An asymmetric Michael addition of α-fluoro-α-nitroalkanes to nitroolefins was developed, and the products were obtained in good chemical yields and with high stereoselectivities. Highly functionalized adducts provided ready access to fluorinated amines and tetrahydropyrimidines in an optically enriched form.
Kwiatkowski, Jacek,Lu, Yixin
supporting information
p. 9313 - 9316
(2014/08/05)

HETEROARYL ACID MORPHOLINONE COMPOUNDS AS MDM2 INHIBITORS FOR THE TREATMENT OF CANCER
The present invention provides MDM2 inhibitor compounds of Formula (I), or the pharmaceutically acceptable salts thereof, wherein the variables are defined above, which compounds are useful as therapeutic agents, particularly for the treatment of cancers. The present invention also relates to pharmaceutical compositions that contain an MDM2 inhibitor of Formula (I).
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Page/Page column 40

(2014/10/04)

Synthesis and applications of quaternized highly branched polyacrylamide as a novel multi-site polymeric phase transfer catalyst
In current study, quaternized highly branched polyacrylamide (HBAA) was synthesized and used as an efficient multi-site polymeric phase transfer catalyst in nucleophilic substitution reactions and also in synthesis of α, β-unsaturated nitriles from reaction of acetonitrile and carbonyl compounds. The quaternized HBAA was synthesized via two steps. First, HBAA was synthesized via self-condensing vinyl polymerization of acrylamide at appropriate molar ratio of monomer to diperiodatocuprate(III). In the second step, 3-acrylamidopropyl trimethylammonium iodide was polymerized on peripheral area of the HBAA in the presence of diperiodatocuprate(III) solution again. The thermal behavior of HBAA and that of the quaternized HBAA were studied by DSC and TGA analysis. This phase transfer catalyst was easily recovered after reaction and reused several times without any loss of activity.
Mahdavi, Hossein,Amirsadeghi, Mehdi
p. 791 - 797
(2013/07/27)

2-Aryl-2-nitroacetates as central precursors to aryl nitromethanes, α-ketoesters, and α-amino acids
Nitroarylacetates are useful small molecular building blocks that act as precursors to α-ketoesters and aryl nitromethanes as well as α-amino acids. Methods were developed that produce each of these compound types in good yields. Two different conditions
Metz, Alison E.,Kozlowski, Marisa C.
p. 717 - 722
(2013/02/25)

Henry reaction of fluorinated nitro compounds
The Henry (nitroaldol) reaction of fluorinated nitro compounds with various aromatic aldehydes and a fluorinated aliphatic aldehyde to give β-fluoro-β-nitroalcohols which bearing a fluorinated quaternary carbon center was reported. The relative configuration of the major diastereoisomer of 2-fluoro-2-nitro-1-(4-nitrophenyl)-3-phenylpropanol (5bf) was determined by X-ray single crystal analysis.
Hu, Huawei,Huang, Yangen,Guo, Yong
experimental part
p. 108 - 114
(2012/02/05)

Palladium-catalyzed nitromethylation of aryl halides: An orthogonal formylation equivalent
An efficient cross-coupling reaction of aryl halides and nitromethane was developed with the use of parallel microscale experimentation. The arylnitromethane products are precursors for numerous useful synthetic products. An efficient method for their direct conversion to the corresponding oximes and aldehydes in a one-pot operation has been discovered. The process exploits inexpensive nitromethane as a carbonyl equivalent, providing a mild and convenient formylation method that is compatible with many functional groups.
Walvoord, Ryan R.,Berritt, Simon,Kozlowski, Marisa C.
supporting information; experimental part
p. 4086 - 4089
(2012/09/22)

Ipso-nitration of arylboronic acids with bismuth nitrate and perdisulfate
An efficient and one pot synthetic method of ipso-nitration of arylboronic acids has been developed. The high efficiency, general applicability, and broader substrate scope including heterocycles and functional groups make this method advantageous. Due to its simplicity, we expect to find application of this method in synthesis.
Manna, Srimanta,Maity, Soham,Rana, Sujoy,Agasti, Soumitra,Maiti, Debabrata
supporting information; experimental part
p. 1736 - 1739
(2012/05/20)

Synthesis of unsymmetrical 3,4-diaryl-3-pyrrolin-2-ones utilizing pyrrole weinreb amides
A regiocontrolled synthesis of unsymmetrical 3,4-diaryl-3-pyrrolin-2-ones has been achieved in three steps from 1,2-diaryl-1-nitroethenes with pyrrole-2-carboxamides (pyrrole Weinreb amides) serving as the key linchpin intermediates. Two different methods for the preparation of the requisite nitroalkenes were investigated: (1) modified Henry reaction between arylnitromethanes and arylimines; and (2) Suzuki-Miyaura cross-coupling reaction of 2-aryl-1-bromo-1-nitroethenes with arylboronic acids. Some difficulty was encountered in the preparation of arylnitromethanes, thus leading to the exploration of a cross-coupling strategy that proved more useful. A Barton-Zard pyrrole cyclocondensation reaction between 1,2-diaryl-1-nitroethenes and N-methoxy-N-methyl-2-isocyanoacetamide gave the corresponding pyrrole Weinreb amides, which were then converted into the desired 3-pyrrolin-2-ones in two steps. Overall, this method allowed for the construction of 3,4-diaryl-3- pyrrolin-2-ones with complete regiocontrol of the substituents with respect to the lactam carbonyl. The utility of this synthetic methodology was demonstrated by the preparation of eight unsymmetrical and symmetrical 3,4-diaryl-3-pyrrolin- 2-ones including the N-H lactam analogue of the selective COX-II inhibitor, rofecoxib.
Greger, Jessica G.,Yoon-Miller, Sarah J. P.,Bechtold, Nathan R.,Flewelling, Scott A.,MacDonald, Jacob P.,Downey, Catherine R.,Cohen, Eric A.,Pelkey, Erin T.
supporting information; experimental part
p. 8203 - 8214
(2011/12/04)

Cascade formation of isoxazoles: Facile base-mediated rearrangement of substituted oxetanes
Give me five! Nitro compounds and oxetan-3-one react through an intriguing cascade sequence to give isoxazole-4-carbaldehydes using inexpensive reagents in a one-pot procedure (see scheme; Ms=methanesulfonyl). A variety of 3-substituted isoxazole-4-carbaldehydes were obtained in high overall yields.
Burkhard, Johannes A.,Tchitchanov, Boris H.,Carreira, Erick M.
supporting information; scheme or table
p. 5379 - 5382
(2011/07/08)

PROCESS FOR THE PREPARATION OF NITRATED AROMATICS AND MIXTURES THEREOF
A process for the preparation of mononitroaromatics and dinitroaromatics, in which a hydrate melt of at least one metal nitrate M(NO3)3 is used as a nitrating medium, it being possible for M to be the metals Fe, Cr, Y, La, Ce, Al, Bi and In, and the metal nitrate having a water content of from 4 to 9 mol of water per M(NO3)3, leads to simplifications of the process and improved yields.
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Page/Page column 4

(2012/01/03)

Kinetic study of proton-transfer reactions of phenylnitromethanes. Implication for the origin of nitroalkane anomaly
Measurements of rate constants and substituent effects for three important elementary steps of proton-transfer reactions of phenylnitromethane were reported. The Hammett ? values for the deprotonation of ArCH2NO 2 with OH-
Ando, Kenichi,Shimazu, Yu,Seki, Natsuko,Yamataka, Hiroshi
experimental part
p. 3937 - 3945
(2011/07/08)

NITRATED HYDROCARBONS, DERIVATIVES, AND PROCESSES FOR THEIR MANUFACTURE
Provided is a process for the formation of nitrated compounds by the nitration of hydrocarbon compounds with dilute nitric acid. Also provided are processes for preparing industrially useful downstream derivatives of the nitrated compounds, as well as novel nitrated compounds and derivatives, and methods of using the derivatives in various applications.
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Page/Page column 27; 29; 33

(2009/12/02)

β-nitroacrylates as key starting materials for the uncatalysed one-pot synthesis of polyfunctionalized dihydroquinoxalinone derivatives, via an anti-Michael reaction
The reaction of o-phenylenediamine with β-nitroacrylates allows the in situ preparation of dihydroquinoxalinones, via an anti-Michael reaction, under uncatalysed reaction conditions.
Ballini, Roberto,Gabrielli, Serena,Palmieri, Alessandro
scheme or table
p. 965 - 967
(2009/10/17)

Selective N-oxidation of aromatic amines to nitroso derivatives using a molybdenum acetylide oxo-peroxo complex as catalyst
The molybdenum acetylide oxo-peroxo complex obtained in situ by the treatment of the corresponding molybdenum acetylide carbonyl complex, CpMo(CO)3(C{triple bond, long}CPh); Cp = η5-C5H5 with H2O2, has been used as an efficient catalyst for selective N-oxidation of primary amines to nitroso derivatives. Excellent amine conversion (up to 100%) and very high selectivity for nitroso compounds (99%) have been obtained using 30% hydrogen peroxide as an oxidant. The oxo peroxo Mo(VI) complex has also been found to be very active for the oxidation of various substituted primary aromatic amines with electron donating as well as electron withdrawing substituents on the aromatic ring.
Biradar, Ankush V.,Kotbagi, Trupti V.,Dongare, Mohan K.,Umbarkar, Shubhangi B.
p. 3616 - 3619
(2008/09/19)

Oxidation of azides by the HOF·CH3CN: A novel synthesis of nitro compounds
The HOF·CH3CN complex, readily prepared by passing F 2 through aqueous acetonitrile, is an exceptionally efficient oxygen transfer agent. It is unique in its capacity to oxidize various azides into the corresponding nitro derivatives. This method requires short reactions times and room temperature or below, and the desired nitro compounds were usually isolated in very good yields. The respective nitroso derivatives are believed to be the intermediates in this reaction. Functional groups such as aromatic rings, ketones, nitriles, halides, alcohols, and esters are tolerated. Sulfides react with HOF·CH3CN usually at the same rate as azides. Amines and olefins, however, react faster, so they have to be protected first. Nitro derivatives with various oxygen isotopes can be made using the labeled H 18OF·CH3CN. In the case of chiral azides the stereochemistry around the nitrogen-bonded carbons is retained.
Carmeli, Mira,Rozen, Shlomo
p. 4585 - 4589
(2007/10/03)

Synthesis of nitroalkanes from alkylhalides under mild and nonaqueous conditions by using polymer supported nitrites
Alkyl halides are efficiently converted to their corresponding nitroalkanes under mild and nonaqueous conditions by using polymer supported nitrites. The polymeric reagent is regenerable.
Zarchi, Mohammad Ali Karimi,Zarei, Amin
p. 309 - 311
(2007/10/03)

Methyltrioxorhenium-catalyzed oxidation of aromatic aldoximes
The first catalytic oxidation of aryl oximes to nitro compounds by means of methyltrioxorhenium and urea hydroperoxide is reported. The formation of carbamates, probably occurring through formation of nitrile oxide intermediates, has been observed from 2,6-disubstituted aryl oximes.
Cardona, Francesca,Soldaini, Gianluca,Goti, Andrea
p. 1553 - 1556
(2007/10/03)

The first conversion of primary alkyl halides to nitroalkanes under aqueous medium
Primary nitroalkanes and α,ω-dinitroalkanes can be easily obtained in aqueous medium by reaction of the corresponding halo derivatives with silver nitrite. The procedure works well with both alkyl bomide and alkyl iodide and proceeds in satisfactory to good yields even in the presence of other functionalities, minimizing the formation of the undesired alkyl nitrites.
Ballini, Roberto,Barboni, Luciano,Giarlo, Guido
p. 6907 - 6908
(2007/10/03)

Nucleophilicities of nitroalkyl anions
The kinetics of the reactions of eight nitroalkyl anions (nitronate anions) with benzhydrylium ions and quinone methides in DMSO and water were investigated photometrically. The second-order rate constants were found to follow a Ritchie constant selectivi
Bug, Thorsten,Lemek, Tadeusz,Mayr, Herbert
p. 7565 - 7576
(2007/10/03)

[VO(H2O)5]H[PMo12O40]- catalyzed nitration of alkanes with nitric acid
[VO(H2O)5]H[PMo12O40], which contains vanadyl counter cations and PMo12O40 3-, can act as a catalyst for the nitration of various alkanes including alkylbenzenes using nitric acid as a nitrating agent in acetic acid at 356 K.
Yamaguchi, Kazuya,Shinachi, Satoshi,Mizuno, Noritaka
p. 424 - 425
(2007/10/03)

Nitration of alkanes with nitric acid by vanadium-substituted polyoxometalates
The nitration of alkanes by using nitric acid as a nitrating agent in acetic acid was efficiently promoted by vanadium-substituted Keggin-type phosphomolybdates such as [H4PVMo11O40], [H5PV2Mo10O40], and [H 6PV3Mo9O40] as catalyst precursors. A variety of alkanes including alkylbenzenes were nitrated to the corresponding nitroalkanes as major products in moderate yields with formation of oxygenated products under mild reaction conditions. The carbon-carbon bond cleavage reactions hardly proceeded. ESR, NMR, and IR spectroscopic data show that the vanadium-substituted polyoxometalate, for example, [H4PVMo 11O40], decomposes to form free vanadium species and [PMo12O40]3- Keggin anion. The reaction mechanism involving a radical-chain path is proposed. The polyoxometalates initially abstract the hydrogen of the alkane to form the alkyl radical and the reduced polyoxometalates. The reduced polyoxometalates subsequently react with nitric acid to produce the oxidized form and nitrogen dioxide. This step would be promoted mainly by the phosphomolybdates, [PMo12O 40]n-, and the vanadium cations efficiently enhance the activity. The nitrogen dioxide promotes the further formation of nitrogen dioxide and an alkyl radical. The alkyl radical is trapped by nitrogen dioxide to form the corresponding nitroalkane.
Shinachi, Satoshi,Yahiro, Hidenori,Yamaguchi, Kazuya,Mizuno, Noritaka
p. 6489 - 6496
(2007/10/03)

From azides to nitro compounds in a few seconds using HOF·CH3CN
HOF·CH3CN, a very efficient oxygen-transfer agent, was reacted with various azides to form the corresponding nitro compounds in excellent yields and in very short reaction times. The respective nitroso derivatives were found to be intermediates in this reaction. When the azides were reacted with MCPBA or DMDO, no reaction took place, and the starting materials were fully recovered. Copyright
Rozen, Shlomo,Carmeli, Mira
p. 8118 - 8119
(2007/10/03)

An efficient nitration of light alkanes and the alkyl side-chain of aromatic compounds with nitrogen dioxide and nitric acid catalyzed by N-hydroxyphthalimide
Nitration of light alkanes and the alkyl side-chain of aromatic compounds with NO2 and HNO3 was successfully achieved by the use of N-hydroxyphthalimide (NHPI) as a catalyst under relatively mild conditions. For example, the nitration of propane with NO2 catalyzed by NHPI at 100 °C for 14 h gave 2-nitropropane in good yield without formation of 1-nitropropane and cleaved products such as nitroethane and nitromethane. Various aliphatic nitroalkanes, which are difficult to prepare by conventional methods, could be selectively obtained by means of the present methodology by using NHPI as the key catalyst. In addition, the side-chain nitration of alkylbenzenes such as toluene was selectively carried out to lead to α-nitrotoluene without the ring nitration. The present reaction provides an efficient selective method for the nitration of light alkanes and alkylbenzenes, which has been very difficult to carry out so far.
Nishiwaki, Yoshiki,Sakaguchi, Satoshi,Ishii, Yasutaka
p. 5663 - 5668
(2007/10/03)

Zeolite-assisted nitration of neat toluene and chlorobenzene with a nitrogen dioxide/molecular oxygen system. Remarkable enhancement of para-selectivity
In the presence of molecular oxygen and HZSM-5, neat toluene reacted with liquid nitrogen dioxide in a regioselective manner at room temperature to yield mononitrotoluenes as the main product, where the para isomer predominated up to 90% and the ortho-para isomer ratio improved to 0.08. Chlorobenzene behaved similarly, giving a para-predominant nitration product.
Peng, Xinhua,Suzuki, Hitomi,Lu, Chunxu
p. 4357 - 4359
(2007/10/03)

Nitration of alkanes with nitric acid catalyzed by N-hydroxyphthalimide
Catalytic nitration of alkanes with nitric acid was first successfully achieved by the use of N-hydroxyphthalimide (NHPI) under mild conditions; the key to the present nitration was found to be the in situ generation of NO2 and phthalimide N-ox
Isozaki,Nishiwaki,Sakaguchi,Ishii
p. 1352 - 1353
(2007/10/03)

A simple and highly efficient procedure for the preparation of aliphatic nitro compounds directly from alcohols
A simple and highly efficient one-pot synthesis of aliphatic nitro compounds from the corresponding alcohols with NaNO2-AcOH-HCl system is described.
Baruah, Apurba,Kalita, Biswajit,Barua, Nabin C.
p. 1064 - 1066
(2007/10/03)

Method for producing nitro compounds
The method provides nitro compounds at a high conversion and selectivity by nitrating substrates under comparatively mild conditions in the absence of catalysts. Organic substrates are nitrated using no catalysts or ozone, but using (1) at least one nitrogen compound selected from N2 O or NO and oxygen. It is advantageous for the nitration reaction to employ a nitrogen compound obtained by a reaction of the nitrogen compound with oxygen, particularly a nitrogen oxide comprising N2 O3 as a main component. Additionally, organic substrates are nitrated using (2) NO2. The substrates include a compound having a methine-carbon atom, and a compound having a methyl group or methylene group in an adjacent position to an aromatic ring.
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(2008/06/13)

A versatile method for the conversion of oximes to nitroalkanes
A convenient oxidation of oximes to nitroalkanes has been developed using oxone in acetonitrile.
Bose, D. Subhas,Vanajatha
p. 4531 - 4535
(2007/10/03)

Antibody-catalyzed retro-aldol reaction
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Flanagan, Mark E.,Jacobsen, John R.,Sweet, Elizabeth,Schultz, Peter G.
p. 6078 - 6079
(2007/10/03)

Preparation and structure determination of 1-benzyl-, 1-methyl- and 1H-5-[(2-nitro-2-phenyl)ethenyl]imidazoles
1-R-5-[(2-Nitro-2-phenyl)ethenyl]imidazoles (R = Bn, Me, H) 6a,b,c were synthesized by the Knoevenagel reaction of the corresponding aldehydes 4a,b,c with phenylnitromethane 5. The E-isomers 6a,b,c were precipitated from the reaction mixture as crystalline compounds in 89, 81 and 60% yields, respectively. Traces of the Z-isomers 6a'b',c' were found in the reaction mixtures but could be obtained in a ratio of 4:3 from the E-form with UV irradiation. The E-forms were more stable and the Z-isomers changed again to the E-isomers in several weeks.
Aulaskari, Paula,Ahlgren, Markku,Rouvinen, Juha,Vainiotalo, Pirjo,Pohjala, Esko,Vepsaelaeinen, Jouko
p. 1345 - 1354
(2007/10/03)

Aromatic Nitration under Neutral Conditions Using Nitrogen Dioxide and Ozone as the Nitrating Agent. Application to Aromatic Acetals and Acylal
Cyclic acetals derived from aromatic carbonyl compounds can be nitrated smoothly with nitrogen dioxide in ice-cooled dichloromethane or acetonitrile in the presence of ozone and magnesium oxide to give ortho- and para-nitro derivatives as the major product in good combined yields, the acetal ring as a protective group remaining almost intact.An acylal derived from benzaldehyde similarly undergoes nitration on the aromatic ring to give an isomeric mixture of three nitro compounds, in which the ortho and meta isomers predominate, while aromatic orthoesters are rapidly decomposed to give simply the parent esters.Ring nitration under neutral conditions has been interpreted in terms of a nonclassical mechanism, in which nitrogen trioxide is involved as the initial electrophile.
Suzuki, Hitomi,Yonezawa, Shuji,Mori, Tadashi
p. 1535 - 1544
(2007/10/03)