cas 3162-29-6, 3,4-Methylenedioxyacetophenone

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AN EFFICIENT PROCESS FOR PREPARATION OF ACYL DERIVATIVES OF ALKYLENEDIOXYBENZENES
The present disclosure provides a process of preparation of compounds of Formula I comprising the step of : reacting an alkylenedioxybenzene compound of Formula II with an acyl halide of Formula III in presence of a solvent, wherein the step of reacting the alkylenedioxybenzene compound of Formula II with the acyl halide of Formula III is effected in presence of an amphoteric oxide and a Lewis acid so as to immediately quench the compound of formula H-X, formed during the course of the reaction, to substantially eliminate degradation of the compound of any of Formula I and II. The present disclosure also provides for process(es) for preparation of compound of Formula IVa, IVb and IVc.
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Paragraph 0098

(2021/08/20)

Synthesis process 3,4 -methylenedioxy phenol
The invention relates to the technical field of compound synthesis, in particular to a synthesis process of 3,4 -methylenedioxy phenol, which comprises the following steps: 3,4 - methylenedioxy acetophenone. The second Catalyst, first solvent was added to the autoclave, and an oxidant was added, and reacted 25 - 50 °C under 4 - 8h, and the first solvent was separated and the solvent was separated. The resulting 3,4 -methylenedioxy phenol acetate is obtained. The second Solvent, sodium hydroxide solution was added to the autoclave, and reacted 20 - 60 °C at 2 - 6h, adjusted pH to 3-6 to obtain 3,4 - methylenedioxy phenol. The method solves the problems that 3,4 -methylenedioxy acetophenone in the prior art is low in yield and large in separation difficulty in preparation of sesame phenol. The process takes the pepper ring as the starting raw material and is divided into three-step reaction synthesis, the raw material conversion rate is high, no other side reaction is avoided, the reaction condition is mild, the production cost is low, and the product quality is better.
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Paragraph 0027-0029; 0033-0035; 0038-0040; 0043-0045; ...

(2021/10/30)

Scalable Aerobic Oxidation of Alcohols Using Catalytic DDQ/HNO3
A selective, practical, and scalable aerobic oxidation of alcohols is described that uses catalytic amounts of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and HNO3, with molecular oxygen serving as the terminal oxidant. The method was successfully applied to the oxidation of a wide range of benzylic, propargylic, and allylic alcohols, including two natural products, namely, carveol and podophyllotoxin. The conditions are also applicable to the selective oxidative deprotection of p-methoxybenzyl ethers.
Arseniyadis, Stellios,Clavier, Louis,Copin, Chloé,Fournier, Jean,Giffard, Jean-Fran?ois,Jean, Alexandre,Katsina, Tania,Macedo Portela Da Silva, Nayane,Tamion, Rodolphe
supporting information
p. 856 - 860
(2020/07/14)

Preparation method of 3, 4-methylenedioxyacetophenone
The invention discloses a preparation method of 3, 4-methylenedioxyacetophenone. The method comprises the following steps: (1) preparation of a diatomite solid acid catalyst: drying diatomite at 110-250 DEG C for more than 5 hours to remove moisture in the diatomite, slowly adding a modifier into the diatomite, and stirring at room temperature for 45-60 minutes to obtain the diatomite solid acid catalyst; and (2) preparation of the 3, 4-methylenedioxyacetophenone: putting the diatomite solid acid catalyst into a reactor containing a solvent, adding raw material 1, 2-methylenedioxy benzene andan acylating agent, carrying out a reaction at 60-120 DEG C for 5-10 h, and carrying out separation and purification to obtain the 3, 4-methylenedioxyacetophenone. The method has the advantages of cheap and easily available raw materials, avoiding of the use of a metal halide catalyst difficult to treat and recycle in the whole process, mild reaction conditions, high yield, less three wastes, andlow cost.
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Paragraph 0021; 0026-0027

(2020/05/08)

Facile preparation of 5-alkyl-1-aryltetrazoles with arenes, acyl chlorides, hydroxylamine, and diphenylphosphoryl azide
Successive treatment of arenes with acyl chlorides and AlCl3, the addition of water and removal of solvent, the reaction with NH2OH?HCl and K2CO3, and the reaction with diphenylphosphoryl azide and DBU under warming conditions gave the corresponding 5-alkyl-1-aryltetrazoles efficiently in good to moderate yields. The present method is one-pot transformation of arenes into 5-alkyl-1-aryltetrazoles using the Friedel-Crafts acylation and the Beckmann rearrangement under transition-metal-free conditions.
Shibasaki, Kaho,Togo, Hideo
p. 1816 - 1830
(2020/11/19)

Synthesis and biological evaluation of 4-(pyridin-4-oxy)-3-(3,3-difluorocyclobutyl)-pyrazole derivatives as novel potent transforming growth factor-β type 1 receptor inhibitors
Inhibition of transforming growth factor β (TGF-β) type 1 receptor (ALK5) provides a feasible approach for the treatment of fibrotic diseases and malignant tumors. In this study, we designed and synthesized a new series of 4-(pyridin-4-oxy)-3-(3,3-difluorocyclobutyl)-pyrazole derivatives, and evaluated biologically as TGF-β type 1 receptor inhibitors. The most potent compound 15r inhibited the ALK5 enzyme and NIH3T3 cell viability with IC50 values of 44 and 42.5 nM, respectively. Compound 15r also displayed better oral plasma exposure and excellent bioavailability than LY-3200882, and in vivo inhibited 65.7% of the tumor growth in a CT26 xenograft mouse model.
Chang, Shaohua,Guo, Zhuang,Li, Xue,Sun, Tianwen,Wang, Hai,Wang, Xiaowei,Wang, Yazhou,Xu, Guofeng,Xu, Tianwei,Yu, Wenying,Yu, Zhuangzhuang,Zhang, Yan,Zhao, Liwen
supporting information

(2020/05/08)

Structure-activity relationships, biological evaluation and structural studies of novel pyrrolonaphthoxazepines as antitumor agents
Microtubule-targeting agents (MTAs) are a class of clinically successful anti-cancer drugs. The emergence of multidrug resistance to MTAs imposes the need for developing new MTAs endowed with diverse mechanistic properties. Benzoxazepines were recently identified as a novel class of MTAs. These anticancer agents were thoroughly characterized for their antitumor activity, although, their exact mechanism of action remained elusive. Combining chemical, biochemical, cellular, bioinformatics and structural efforts we developed improved pyrrolonaphthoxazepines antitumor agents and their mode of action at the molecular level was elucidated. Compound 6j, one of the most potent analogues, was confirmed by X-ray as a colchicine-site MTA. A comprehensive structural investigation was performed for a complete elucidation of the structure-activity relationships. Selected pyrrolonaphthoxazepines were evaluated for their effects on cell cycle, apoptosis and differentiation in a variety of cancer cells, including multidrug resistant cell lines. Our results define compound 6j as a potentially useful optimized hit for the development of effective compounds for treating drug-resistant tumors.
Brindisi, Margherita,Ulivieri, Cristina,Alfano, Gloria,Gemma, Sandra,de Asís Balaguer, Francisco,Khan, Tuhina,Grillo, Alessandro,Chemi, Giulia,Menchon, Grégory,Prota, Andrea E.,Olieric, Natacha,Lucena-Agell, Daniel,Barasoain, Isabel,Diaz, J. Fernando,Nebbioso, Angela,Conte, Mariarosaria,Lopresti, Ludovica,Magnano, Stefania,Amet, Rebecca,Kinsella, Paula,Zisterer, Daniela M.,Ibrahim, Ola,O'Sullivan, Jeff,Morbidelli, Lucia,Spaccapelo, Roberta,Baldari, Cosima,Butini, Stefania,Novellino, Ettore,Campiani, Giuseppe,Altucci, Lucia,Steinmetz, Michel O.,Brogi, Simone
p. 290 - 320
(2018/11/24)

Hydrogen bond donor solvents enabled metal and halogen-free Friedel–Crafts acylations with virtually no waste stream
We have developed a metal and halogen-free Friedel–Crafts acylation protocol with virtually no waste stream generation. We propose a hydrogen bonding donor solvent will form a hydrogen bonding network and may provide significant rate enhancement for Friedel–Crafts reactions. Trifluoroacetic acid is one of the strongest H-bond donor solvents, which is also volatile and can be easily recovered by distillation without need for reaction workup. Our protocol is a ‘green’ Friedel–Crafts acylation process: 1) the catalyst can be recovered and reused; 2) using halogen free starting material (carboxylic acids anhydride or carboxylic acids); 3) no need for aqueous reaction work-up; 4) minimum or no waste steam generation.
Liu, Guangchang,Xu, Bo
supporting information
p. 869 - 872
(2018/02/09)

Biomimetic Oxidative Deamination Catalysis via ortho-Naphthoquinone-Catalyzed Aerobic Oxidation Strategy
An ortho-naphthoquinone-catalyzed oxidative deamination reaction has been developed where the molecular oxygen and water serve as the sole oxidant and nucleophile. The current aerobic deamination reaction proceeds via the ketimine formation between ortho-naphthoquinones and amines followed by the prototropic rearrangement and hydrolysis by water, representing a biomimetic oxidative deamination of amine species in the human body by the liver and kidneys. The compatibility of ortho-naphthoquinone organocatalysts with molecular oxygen and water opens up a new biomimetic catalyst system that can function as versatile deaminases for a variety of amine-containing molecules such as amino acids and DNA nuclear bases.
Golime, Gangadhararao,Bogonda, Ganganna,Kim, Hun Young,Oh, Kyungsoo
p. 4986 - 4990
(2018/05/14)

Piperonal preparation method
The invention discloses a piperonal preparation method. In the prior art, the method for preparing piperonal by using 1,3-benzodioxole as a raw material is used, wherein a large amount of hydrochloric acid is used so as to corrode the equipment and produce the environmental pollution problem, the reaction post-treatment is complicated, and more waste can be produced. The piperonal preparation method of the present invention comprises: 1) preparing 3,4-methylenedioxyacetophenone by using 1,3-benzodioxole and an acylation reagent as raw materials and using a supported aluminum chloride or zinc chloride catalyst through a Friedel-Crafts reaction; and 2) oxidizing the 3,4-methylenedioxyacetophenone by using a cuprous salt as a catalyst through a catalytic oxidation reaction to obtain the piperonal. According to the present invention, the piperonal preparation method has the total piperonal yield of up to about 93%, and has advantages of short reaction step, less by-product, high yield, easily available raw material, simple process, environment protection and low piperonal preparation cost, wherein the catalyst of the Friedel-Crafts reaction can be recycled.
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Paragraph 0031; 0032

(2018/03/01)

Palladium-Catalyzed Chemo- and Enantioselective C?O Bond Cleavage of α-Acyloxy Ketones by Hydrogenolysis
A chemoselective C?O bond cleavage of the ester alkyl side-chain of α-acyloxy ketones was realized for the first time by a highly efficient palladium-catalyzed hydrogenolysis (S/C=6000, the highest catalytic efficiency by far). Furthermore, a kinetic resolution of α-acyloxy ketones was first developed by enantioselective hydrogenolysis with good yields and up to 99 % ee.
Chen, Jianzhong,Zhang, Zhenfeng,Liu, Delong,Zhang, Wanbin
supporting information
p. 8444 - 8447
(2016/07/19)

Development of new highly potent imidazo[1,2-b[pyridazines targeting Toxoplasma gondii calcium-dependent protein kinase 1
Using a structure-based design approach, we have developed a new series of imidazo[1,2-b]pyridazines, targeting the calcium-dependent protein kinase-1 (CDPK1) from Toxoplasma gondii. Twenty derivatives were thus synthesized. Structure-activity relationships and docking studies confirmed the binding mode of these inhibitors within the ATP binding pocket of TgCDPK1. Two lead compounds (16a and 16f) were then identified, which were able to block TgCDPK1 enzymatic activity at low nanomolar concentrations, with a good selectivity profile against a panel of mammalian kinases. The potential of these inhibitors was confirmed in vitro on T. gondii growth, with EC50 values of 100 nM and 70 nM, respectively. These best candidates also displayed low toxicity to mammalian cells and were selected for further in vivo investigations on murine model of acute toxoplasmosis.
Moine, Espérance,Dimier-Poisson, Isabelle,Enguehard-Gueiffier, Cécile,Logé, Cédric,Pénichon, Mélanie,Moiré, Nathalie,Delehouzé, Claire,Foll-Josselin, Beátrice,Ruchaud, Sandrine,Bach, Stéphane,Gueiffier, Alain,Debierre-Grockiego, Fran?oise,Denevault-Sabourin, Caroline
p. 80 - 105
(2015/11/02)

Catalysis of the acylation of aromatic derivatives by metallic tosylates
A series of metallic tosylates were prepared by ultrasonic metal activation and were further used as efficient catalysts for the acylation of aromatic derivatives.
Morizur, Vincent,Szafranek, Jessica,Bonhomme, Dominique,Olivero, Sandra,Desmurs, Jean Roger,Du?ach, Elisabet
supporting information
p. 6813 - 6817
(2015/08/24)

Design, synthesis and pharmacology of 1,1-bistrifluoromethylcarbinol derivatives as liver X receptor β-selective agonists
A novel series of 1,3-bistrifluoromethylcarbinol derivatives that act as liver X receptor (LXR) β-selective agonists was discovered. Structure-activity relationship studies led to the identification of molecule 62, which was more effective (Emax) and selective toward LXRβ than T0901317 and GW3965. Furthermore, 62 decreased LDL-C without elevating the plasma TG level and significantly suppressed the lipid-accumulation area in the aortic arch in a Bio F1B hamster fed a diet high in fat and cholesterol. We demonstrated that our LXRβ agonist would be potentially useful as a hypolipidemic and anti-atherosclerotic agent. In this manuscript, we report the design, synthesis and pharmacology of 1,3-bistrifluoromethylcarbinol derivatives.
Koura, Minoru,Matsuda, Takayuki,Okuda, Ayumu,Watanabe, Yuichiro,Yamaguchi, Yuki,Kurobuchi, Sayaka,Matsumoto, Yuuki,Shibuya, Kimiyuki
p. 2668 - 2674
(2015/06/08)

Divergent and concise total syntheses of dihydrochalcones and 5-deoxyflavones recently isolated from Tacca species and Mimosa diplotricha
Dihydrochalcones and 5-deoxyflavones are types of compounds possessing various biologically interesting properties. Herein, we report the concise and divergent total syntheses of several naturally occurring dihydrochalcones and 5-deoxyflavones from readily available starting materials. The divergent strategy is based around manipulation of a common chalcone scaffold and features application of Algar-Flynn-Oyamada oxidation and benzoquinone C-H activation methodologies. These are the first reported total syntheses of these biologically interesting compounds and the concise and flexible route should be readily amenable to future analogue generation. Furthermore, this work provides an illustration of the utility of divergent synthesis for the expedient and step-economical preparation of natural product libraries.
Sum, Tze Han,Sum, Tze Jing,Stokes, Jamie E.,Galloway, Warren R.J.D.,Spring, David R.
p. 4557 - 4564
(2015/06/08)

Simple, copper(I)-catalyzed oxidation of benzylic/allylic alcohols to carbonyl compounds: Synthesis of functionalized cinnamates in one pot
An environmentally benign [Cu(I)]-catalyzed oxidation of activated (benzylic/allylic) alcohols to the corresponding carbonyl compounds is presented. Interestingly, the reaction was also compatible with benzylic alcohols containing ortho-bromo substituents on the aromatic ring without competing with the expected intermolecular Buchwald coupling. Significantly, the catalytic system enables the synthesis of cinnamate-esters in a sequential domino one-pot fashion via oxidation followed by Wittig-Horner protocol. Copyright
Reddy, Alavala Gopi Krishna,Mahendar, Lodi,Satyanarayana, Gedu
supporting information
p. 2076 - 2087
(2014/07/07)

Synthesis and characterization of novel benzo[d][1,3]dioxole gathered pyrazole derivatives and their antimicrobial evaluation
Benzo[d][1,3]dioxole gathered pyrazole derivatives (4a-i) were synthesized by the reaction of chalcones with phenyl hydrazine in presence of absolute alcohol as a solvent. Chalcones were prepared by the Claisen-Schmidt reaction between 1-(benzo[d][1,3]dioxol-5-yl)ethanone (2) and substituted aromatic aldehydes. The synthesized compounds were characterized by spectral and elemental analysis data. Furthermore, Benzo[ d][1,3]dioxole gathered pyrazole derivatives (4a-i) were evaluated for their in vitro antimicrobial activity. Among the newly synthesized compounds 4a, 4c, 4 g and 4 h showed the excellent antifungal activity and as well as 4a and 4d showed the excellent antibacterial activity when compared to other compounds. Springer Science+Business Media 2014.
Umesha, Basavaiah,Basavaraju, Yeriyur Basavaiah
p. 3744 - 3751
(2014/08/05)

Hypervalent iodine mediated direct one pot transformation of aldehydes to ketones
An environmentally benign, step economical synthesis of ketones directly from aldehydes has been developed using hypervalent iodine as an oxidant. The key features of this protocol are its mild conditions without the use of any heavy and toxic metals for the synthesis of a wide range of ketones. the Partner Organisations 2014.
Sagara, Prateep Singh,Chebolu, Rajesh,Bahuguna, Ashish,Ravikumar
p. 15011 - 15013
(2014/04/17)

Mild and efficient nickel-catalyzed heck reactions with electron-rich olefins
A new efficient protocol for the nickel-catalyzed Heck reaction of aryl triflates with vinyl ethers is presented. Mild reaction conditions that equal those of the corresponding palladium-catalyzed Heck reaction are applied, representing a practical and more sustainable alternative to the conventional regioselective arylation of vinyl ethers. A catalytic system comprised of Ni(COD)2 and 1,1″-bis(diphenylphosphino)ferrocene (DPPF) in combination with the tertiary amine Cy2NMe proved effective in the olefination of a wide range of aryl triflates. Both electron-deficient and electron-rich arenes proved compatible, and the corresponding aryl methyl ketone could be secured after hydrolysis in yields approaching quantitative. Good functional group tolerance was observed matching the characteristics of the analogous Pd-catalyzed Heck reaction. The high levels of catalytic activity were explained by the intermediacy of a cationic nickel(II) complex potentially responsible for the successive β-hydride elimination and base promoted catalyst regeneration. Although these elementary reactions are normally considered challenging, DFT calculations suggested this pathway to be favorable under the applied reaction conditions.
Gogsig, Thomas M.,Kleimark, Jonatan,Nilsson Lill, Sten O.,Korsager, Signe,Lindhardt, Anders T.,Norrby, Per-Ola,Skrydstrup, Troels
p. 443 - 452
(2012/03/07)

Hydrogen-bonding-promoted oxidative addition and regioselective arylation of olefins with aryl chlorides
The first, general, and highly efficient catalytic system that allows a wide range of activated and unactivated aryl chlorides to couple regioselectively with olefins has been developed. The Heck arylation reaction is likely to be controlled by the oxidative addition of ArCl to Pd(0). Hence, an electron-rich diphosphine, 4-MeO-dppp, was introduced to facilitate the catalysis. Solvent choice is critical, however; only sluggish arylation is observed in DMF or DMSO, whereas the reaction proceeds well in ethylene glycol at 0.1-1 mol % catalyst loadings, displaying excellent regioselectivity. Mechanistic evidence supports that the arylation is turnover-limited by the oxidative addition step and, most importantly, that the oxidative addition is accelerated by ethylene glycol, most likely via hydrogen bonding to the chloride at the transition state as shown by DFT calculations. Ethylene glycol thus plays a double role in the arylation, facilitating oxidative addition and promoting the subsequent dissociation of chloride from Pd(II) to give a cationic Pd(II)-olefin species, which is key to the regioselectivity observed.
Ruan, Jiwu,Iggo, Jonathan A.,Berry, Neil G.,Xiao, Jianliang
supporting information; experimental part
p. 16689 - 16699
(2011/02/23)

One-pot two-step oxidative cleavage of 1,2-arylalkenes to aryl ketones instead of arylaldehydes in an aqueous medium: A complementary approach to ozonolysis
A new approach has been developed for a one-pot and selective oxidative cleavage of aryl- and 1,2-diarylalkenes leading to one-carbon shorter aryl ketones; thereby, providing a complementary approach to classical ozonolysis. The methodology was applicable to diverse aromatic and polyaromaticarylalkenes bearing electron-donating or -withdrawing groups on the aromatic ring. The protocol also provided a useful one-pot oxidative cleavage-condensation sequence, which could potentially have important applications in natural product total synthesis. A one-pot, two-step approach has been achieved for the oxidative cleavage of 1,2-disubstituted arylalkenes into the corresponding aryl ketones instead of arylaldehydes (see scheme; NIS = N-iodosuccinimide; CTAB = cetyltrimethylammonium bromide; PDC/TBHP = pyridinium dichromate/tert-butyl hydroperoxide). The methodology also led to a valuable one-pot oxidative cleavage-condensation reaction that has widespread utility in the total synthesis of natural products.
Sharma, Naina,Sharma, Abhishek,Kumar, Rakesh,Shard, Amit,Sinha, Arun K.
supporting information; experimental part
p. 6025 - 6032
(2011/02/23)

Biocatalytic promiscuity of lipase in chemoselective oxidation of aryl alcohols/acetates: a unique synergism of cal-b and [hmim]br for the metal-free h2o2 activation
A unique synergistic combination of lipase and Ionic liquid [hmlm]Br Is reported for metal-free H2O2 activation, which is the first example of blocatalytlc promiscuity of CAL-B for chemoselectlve oxidation of aryl alcohols/acetates. The catalytic system exhibits excellent functional group compatibility under neutral conditions besides reusability up to ten cycles thereby making the process economically and environmentally viable.
Sharma, Upendra K.,Sharma, Nandini,Kumar, Rakesh,Kumar, Rajesh,Sinha, Arun K.
supporting information; experimental part
p. 4846 - 4848
(2010/01/16)

The palladium-catalyzed aerobic kinetic resolution of secondary alcohols: Reaction development, scope, and applications
The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23°C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-toexcellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.
Ebner, David C.,Bagdanoff, Jeffrey T.,Ferreira, Eric M.,McFadden, Ryan M.,Caspi, Daniel D.,Trend, Raissa M.,Stoltz, Brian M.
supporting information; experimental part
p. 12978 - 12992
(2010/06/19)

Ionic liquid promoted selective debromination of α-bromoketones under microwave irradiation
The debromination of α-bromoketones with an easily accessible ionic liquid, 1-methyl-3-pentylimidazolium tetrafluoroborate, [pmIm]BF4 under microwave irradiation has been investigated. By controlling the reaction time gem-α-dibromoketones are selectively debrominated to either monobromo or debromoketones. The α-monobromo- and α-monoiodoketones are dehalogenated while the corresponding chloroketones remain inert. The activated vic-bromoacetates are converted to the corresponding (E)-alkenes by the same procedure. These reactions do not require any organic solvent, any metal or any conventional reducing agent. The ionic liquid works here as catalyst as well as reaction medium and is recycled without any appreciable loss of its catalytic efficiency.
Ranu, Brindaban C.,Chattopadhyay, Kalicharan,Jana, Ranjan
p. 155 - 159
(2007/10/03)

A new paradigm for carbon-carbon bond formation: Aerobic, copper-templated cross-coupling
Thiol esters and boronic acids react to produce ketones under aerobic conditions in the presence of catalytic quantities of a CuI or CuII salt. The reaction occurs at reasonable rates between room temperature and 50 °C at neutral pH using thiol esters derived from bulky 2° amides of thiosalicylamides such as those based on N-tert-butyl-2-mercaptobenzamide. In this mechanistically unprecedented reaction system, the carbon-carbon bond formation occurs through templating of the thiol ester and the boronic acid at copper; the system is rendered catalytic in copper under the aerobic conditions. Copyright
Villalobos, Janette M.,Srogl, Jiri,Liebeskind, Lanny S.
p. 15734 - 15735
(2008/09/20)

ARYLAMINE KETONES, THEIR PREPARATION METHODS, THE PHARMACEUTICAL COMPOSITIONS CONTAINING THEM AND THEIR USE
Disclosed Arylamine ketones of formula (I), their preparation methods, the pharmaceutical compositions containing them and their use in preventing and/or treating the diseases related to the plaque-activating factors, especially in anti-inflammation and immunization, more especially in the treatment of the acute or chronic inflammation, such as, osteoarthritis, oarthritis deformans, etc..
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(2010/11/27)

Multicatalytic processes using diverse transition metals for the synthesis of alkenes
A series of cascade processes for the synthesis of alkenes from alcohols is described. Each individual step is catalyzed with a specific transition metal complex. The oxidation-methylenation one-pot procedure took place in the presence of a palladium and a rhodium catalyst to produce the desired terminal alkenes in high yields. A methylenation-ring-closing metathesis allowed the synthesis of cyclic alkenes from carbonyl derivatives, using the second-generation metathesis catalyst. Finally, an oxidation-methylenation-RCM process that involves up to three different transition metal catalysts in the same vessel is presented. Copyright
Lebel, Helene,Paquet, Valrie
p. 11152 - 11153
(2007/10/03)

Photolysis of α-azidoacetophenones: Direct detection of triplet alkyl nitrenes in solution
We report the first detection of triplet alkyl nitrenes in fluid solution by laser flash photolysis of α-azido acetophenone derivatives, 1. Azides 1 contain an intramolecular triplet sensitizer, which ensures formation of the triplet alkyl nitrene by bypassing the singlet nitrene intermediate. At room temperature, azides 1 cleave to form benzoyl and methyl azide radicals in competition with triplet energy transfer to form triplet alkyl nitrene. The major photoproduct 3 arises from interception of the triplet alkyl nitrene with benzoyl radicals. The triplet alkyl nitrene intermediates are also trapped with molecular oxygen to yield the corresponding 2-nitrophenylethanone. Laser flash photolysis of 1 reveals that the triplet alkyl nitrenes have absorption around 300 nm. The triplet alkyl nitrenes were further characterized by obtaining their UV and IR spectra in argon matrices. 13C and 15N isotope labeling studies allowed us to characterize the C-N stretch of the nitrene intermediate at 1201 cm-1.
Singh, Pradeep N. D.,Mandel, Sarah M.,Robinson, Rachel M.,Zhu, Zhendong,Franz, Roberto,Ault, Bruce S.,Gudmundsdottir, Anna D.
p. 7951 - 7960
(2007/10/03)

A novel preparation of methyl ketones through one-carbon homologation of aldehydes
A novel two-step aldehyde homologation procedure for the preparation of methyl ketones has been developed, which involves the use of 1,1-dibromo-1-alkenes as precursors and zinc metal as mediator in near-critical water.
Wang, Lei,Li, Pinhua,Yan, Jincan,Wu, Zhongzhi
p. 4685 - 4688
(2007/10/03)

A "Hard/Soft" Mismatch Enables Catalytic Friedel-Crafts Acylations
(Equation Presented) Cationic complexes of Pt(II) and other late transition metals efficiently catalyze Friedel-Crafts acylations of moderately activated arenes by carboxylic acid anhydrides. The nature of the catalytically relevant species formed from (PhCN)2PtCl2 and AgSbF6 and their interactions with the substrates are studied by NMR and ESI-MS.
Fuerstner, Alois,Voigtlaender, David,Schrader, Wolfgang,Giebel, Dirk,Reetz, Manfred T.
p. 417 - 420
(2007/10/03)

Electro-oxidative kinetic resolution of sec-alcohols by using an optically active N-oxyl mediator
Electro-oxidative kinetic resolution of sec-alcohols mediated with a catalytic amount of an optically active N-oxyl was performed by use of a simple undivided cell under constant current conditions. The selectivity factor (S-value) increased remarkably when the reaction was performed at lower temperatures. The optically active N-oxyl was recovered and used repeatedly without any change in efficiency and selectivity. (C) 2000 Elsevier Science Ltd.
Kuroboshi,Yoshihisa,Cortona,Kawakami,Gao,Tanaka
p. 8131 - 8135
(2007/10/03)

A concise route to novel 1-aryl and 1-pyridyl-2-azabicyclo[2.1.1]hexanes
A number of novel 1-aryl and 1-pyridyl-2-azabicyclo[2.1.1]hexane derivatives were prepared by an intramolecular [2+2] photocycloaddition in the presence of acetophenone as the sensitizer. Substitution of the azabicyclo[2.1.1]hexane ring was accomplished by appropriate choice of the heteroaryl ketone and allylamine starting materials. Several aryl 9a-e, g and pyridyl analogs 9h-l were prepared by this method. The structures of 9a and 9i were verified by X-ray crystallography. Several of the photoproducts 9 were converted into the corresponding N-Me and N-H 2,4-methanonicotine analogs 4 by reduction or hydrolysis of the N-carboethoxy group.
Piotrowski, David W.
p. 1091 - 1093
(2007/10/03)

A Facile Synthesis of Aldehyde and Ketone via Sonochemical Barbier Reaction and Oxidation
Methyl ketone is prepared by a sonochemical Barbier reaction of methyl iodide, magnesium powder and aldehyde in Benzene/THF (9/1) solvent in a commercial ultrasonic cleaning bath (39 kHz), followed by the addition of N-chlorosuccinimide (NCS) as an oxidizing agent.
Lee, Adam Shih-Yuan,Kung, Chih-Chun
p. 65 - 69
(2007/10/03)

Diarylspiro[2.4]heptenes as orally active, highly selective cyclooxygenase-2 inhibitors: Synthesis and structure-activity relationships
A novel series of 5,6-diarylspiro[2.4]hept-5-enes was shown to provide highly potent and selective cyclooxygenase-2 (COX-2) inhibitors. A study of structure-activity relationships in this series suggests that 3,4- disubstituted phenyl analogs are generally more selective than 4-substituted phenyl analogs and that replacement of the methyl sulfone group on the 6- phenyl ring with a sulfonamide moiety results in compounds with superior in vivo pharmacological properties, although with lower COX-2 selectivity. Several compounds have been shown to possess promising pharmacological properties in adjuvant-induced arthritis and edema analgesia models. The absence of gastrointestinal (GI) toxicity at 200 mpk of several selected compounds in rats and mice corresponds well with the weak potency for inhibition of COX-1 observed in the enzyme assay. Methyl sulfone 55 and sulfonamide 24 were shown to have superior in vivo pharmacological profiles, low GI toxicity, and good oral bioavailability and duration of action.
Huang, Horng-Chih,Li, James J.,Garland, Danny J.,Chamberlain, Timothy S.,Reinhard, Emily J.,Manning, Robert E.,Seibert, Karen,Koboldt, Carol M.,Gregory, Susan A.,Anderson, Gary D.,Veenhuizen, Amy W.,Zhang, Yan,Perkins, William E.,Burton, Earl G.,Cogburn, J. Nita,Isakson, Peter C.,Reitz, David B.
p. 253 - 266
(2007/10/03)

Studies on the Synthesis of Heterocyclic Compounds. XVI. Cleavage of 1,3-Benzodioxoles and -Benzoxathioles by Sodium Iodide-Acyl Chloride
The cleavage reaction of ethereal and thioethereal bonds with sodium iodide and acyl chloride has been studied.In all the 1,3-benzodioxoles and -benzoxathioles studied, the opening of the heterocyclic ring with formation of 1,2-diacetoxybenzene or 2-hydroxythiophenol diacetic acid ester and gem-diiodoalkanes and iodoalkenes has been observed.The structure of newly prepared compounds has been determined by analytical and spectroscopic data or comparison with authentic samples.
Corda, Luciana,Fadda, Anna Maria,Maccioni, Antonio,Maccioni, Anna Maria,Podda, Gianni
p. 311 - 314
(2007/10/02)

Reactions of α,β-Unsaturated Ketones with Nucleophiles
Selective loss of an acetyl group from 4-acetoxy-3-methoxycarbonyl or acetyl-4-substitutedphenylbut-3-ene-2-ones is shown to occur during their reactions with nucleophiles.
Akhtar, M. Shamim,Seth, M.,Bhaduri, A. P.
p. 71 - 72
(2007/10/02)

Utilization of protopine and related alkaloids. XVII. Spectroscopic studies on the ten-membered ring conformations of protopine and α-allocryptopine
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Takahashi,Iguchi,Onda
p. 4775 - 4782
(2007/10/02)

Novel Oxidation of Tetrasubstituted Furans by Pyridinium Chlorochromate
A novel oxidation of tetrasubstituted furans with pyrimidinium chlorochromate has been studied and this has led to a convenient synthesis of 4-acetoxy-3-acetyl- or methoxycarbonyl-4-substituted phenylbut-3-en-2-one.
Akhtar, Mohammed Shamim,Seth, Manju,Bhaduri, Amiya Prasad
p. 1323 - 1324
(2007/10/02)

New Syntheses of Antitumor Benzophenanthridine Alkaloids: Nitidine and Fagaronine
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Ishii, Hisashi,Ishikawa, Tsutomu,Chen, Ih-Sheng,Ichikawa, Yuh-Ichiro
p. 711
(2007/10/02)

Studies on the chemical constituents of rutaceous plants. XLIX. Development of a versatile method for the synthesis of antitumor-active benzo[c]phenanthridine alkaloids. (1). Preparation of various 2,4-bisaryl-4-oxobutyronitriles and 2,4-bisaryl-4-oxobutyramides
For the sake of establishment of a versatile synthetic method for benzo[c]phenanthridine alkaloids, improvement of the Robinson synthetic method was examined. Thirteen chalcones (7a-m) were prepared by condensation of two acetophenone derivatives (15 and 16) with eleven benzaldehyde derivatives (19a-k) as fundamental starting materials. Hydrocyanation of these chalcones (7a-1) except one (7m) gave the corresponding 2,4-bisaryl-4-oxobutyronitriles (8a-1). Eleven 2,4-bisaryl-4-oxobutyramides (9a-k) were also prepared.
Ishii,Ishikawa,Deushi,et al.
p. 3024 - 3038
(2007/10/02)

Studies on the chemical constituents of rutaceous plants. L. Development of a versatile method for the synthesis of antitumor-active benzo[c]phenanthridine alkaloids. (2). Preparation of 2-aryl-1-tetralone derivatives
The synthetic pathway from 2,4-bisaryl-4-oxobutyramide (3) to 2-aryl-1-tetralone (4), which is the key intermediate in the Robinson synthesis of antitumor-active benzo[c]phenanthridine alkaloids was improved. Treatment of the model keto-amide (3a) under the reported basic conditions gave γ-keto-α,β-unsaturated acid (9) and degradation products. Reduction of the 2,4-bisaryl-4-oxobutyramide (3) with sodium borohydride gave 2,4-bisaryl-4-hydroxybutyramide (16) which could easily be hydrogenolyzed to give 2,4-bisarylbutyramide (15). However, this transformation also tended to give a γ-lactam derivative (17), unfortunately. We succeeded in the direct hydrogenolysis of the 2,4-bisaryl-4-oxobutyramide (3) to the 2,4-bisarylbutyramide (15), which could be hydrolyzed to the corresponding acid (5) without difficulty. The direct hydrolysis of the 2,4-bisaryl-4-oxobutyronitrile (2) to the 2,4-bisaryl-4-oxobutyric acid (6) as reported by Cheng et al. was also examined. Ten 2-aryl-1-tetralones (4) required as starting materials for syntheses of various benzo[c]phenanthridine alkaloids were prepared.
Ishii,Kawanabe,Harada,et al.
p. 3039 - 3055
(2007/10/02)

Reaction of Aryl and Vinyl Halides with Zerovalent Nickel-Preparative Aspects and the Synthesis of Alnusone
Zerovalent nickel complexes such as bis(1,5-cyclooctadiene)nickel and tetrakis(triphenylphosphine)nickel react rapidly with aryl and vinyl halides to produce the symmetrical coupling products, a low-temperature analogue of the Ullman reaction.The reaction proceeds through oxidative addition of the organic halide to Ni(0), and the reactivity of the Ni(II)intermediates has been examined.Arylnickel halide complexes decompose rapidly to biaryls in DMF.The coupling of simple vinyl halides proceeds with isomerization of the double bond but 3-haloacrylates give efficient co upling with retention of geometry.Cyclizations to form ortho-bridged biaryls are efficient in simple cases (6-, 7-, 8-, 9-, 10-, and 14-membered rings) but fail with an ortho-disubstituted case.The 13-membered meta-bridged cyclic biphenyl, alnusone, is prepared efficiently with the crucial aryl halide coupling to form the ring proceeding in 50percent yield.A side reaction promoted by the presence of protons and with certain ortho-substituted aryl halides is reduction of the aryl halide to the arene.This process can be enhanced by deliberate addition of acid during reaction with Ni(0) and a series of aryl halides underwent succesful reduction.
Semmelhack, M.F.,Helquist, Paul,Jones, L.D.,Keller, Leonard,Mendelson L.,et al.
p. 6460 - 6471
(2007/10/02)

NEW METHODS AND REAGENTS IN ORGANIC SYNTHESIS. 11. REACTION OF TRIMETHYLSILYLDIAZOMETHANE WITH AROMATIC ALDEHYDES
Trimethylsilyldiazomethane adds to aromatic aldehydes in the presence of triethylamine in methanolic solution to give epoxides and homologous compounds.
Hashimoto, Norio,Aoyama, Toyohiko,Shioiri, Takayuki
p. 975 - 979
(2007/10/02)