cas 826-55-1, 2-Methyl-2-phenylpropionic acid

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Palladium-Catalyzed Distal m-C-H Functionalization of Arylacetic Acid Derivatives
Herein, we present m-C-H olefination on derivatives of phenylacetic acids by tethering with a simple nitrile-based template through palladium catalysis. Notably, the versatility of the method is evaluated with a wide range of phenylacetic acid derivatives for obtaining the meta-olefination products in fair to excellent yields with outstanding selectivities under mild conditions. Significantly, the present strategy is successfully exemplified for the synthesis of drugs/natural product analogues (naproxen, ibuprofen, paracetamol, and cholesterol).
Srinivas, Dasari,Satyanarayana, Gedu
supporting information
p. 7353 - 7358
(2021/10/01)

Desulfonylative Electrocarboxylation with Carbon Dioxide
Electrocarboxylation of organic halides is one of the most investigated electrochemical approaches for converting thermodynamically inert carbon dioxide (CO2) into value-added carboxylic acids. By converting organic halides into their sulfone derivatives, we have developed a highly efficient electrochemical desulfonylative carboxylation protocol. Such a strategy takes advantage of CO2as the abundant C1 building block for the facile preparation of multifunctionalized carboxylic acids, including the nonsteroidal anti-inflammatory drug ibuprofen, under mild reaction conditions.
Zhong, Jun-Song,Yang, Zi-Xin,Ding, Cheng-Lin,Huang, Ya-Feng,Zhao, Yi,Yan, Hong,Ye, Ke-Yin
supporting information
p. 16162 - 16170
(2021/09/02)

Suppressing carboxylate nucleophilicity with inorganic salts enables selective electrocarboxylation without sacrificial anodes
Although electrocarboxylation reactions use CO2as a renewable synthon and can incorporate renewable electricity as a driving force, the overall sustainability and practicality of this process is limited by the use of sacrificial anodes such as magnesium and aluminum. Replacing these anodes for the carboxylation of organic halides is not trivial because the cations produced from their oxidation inhibit a variety of undesired nucleophilic reactions that form esters, carbonates, and alcohols. Herein, a strategy to maintain selectivity without a sacrificial anode is developed by adding a salt with an inorganic cation that blocks nucleophilic reactions. Using anhydrous MgBr2as a low-cost, soluble source of Mg2+cations, carboxylation of a variety of aliphatic, benzylic, and aromatic halides was achieved with moderate to good (34-78%) yields without a sacrificial anode. Moreover, the yields from the sacrificial-anode-free process were often comparable or better than those from a traditional sacrificial-anode process. Examining a wide variety of substrates shows a correlation between known nucleophilic susceptibilities of carbon-halide bonds and selectivity loss in the absence of a Mg2+source. The carboxylate anion product was also discovered to mitigate cathodic passivation by insoluble carbonates produced as byproducts from concomitant CO2reduction to CO, although this protection can eventually become insufficient when sacrificial anodes are used. These results are a key step toward sustainable and practical carboxylation by providing an electrolyte design guideline to obviate the need for sacrificial anodes.
Corbin, Nathan,Lazouski, Nikifar,Manthiram, Karthish,Steinberg, Katherine,Yang, Deng-Tao
p. 12365 - 12376
(2021/10/08)

Achiral Derivatives of Hydroxamate AR-42 Potently Inhibit Class i HDAC Enzymes and Cancer Cell Proliferation
AR-42 is an orally active inhibitor of histone deacetylases (HDACs) in clinical trials for multiple myeloma, leukemia, and lymphoma. It has few hydrogen bond donors and acceptors but is a chiral 2-arylbutyrate and potentially prone to racemization. We report achiral AR-42 analogues incorporating a cycloalkyl group linked via a quaternary carbon atom, with up to 40-fold increased potency against human class I HDACs (e.g., JT86, IC50 0.7 nM, HDAC1), 25-fold increased cytotoxicity against five human cancer cell lines, and up to 70-fold less toxicity in normal human cells. JT86 was ninefold more potent than racAR-42 in promoting accumulation of acetylated histone H4 in MM96L melanoma cells. Molecular modeling and structure-activity relationships support binding to HDAC1 with tetrahydropyran acting as a hydrophobic shield from water at the enzyme surface. Such potent inhibitors of class I HDACs may show benefits in diseases (cancers, parasitic infections, inflammatory conditions) where AR-42 is active.
Tng, Jiahui,Lim, Junxian,Wu, Kai-Chen,Lucke, Andrew J.,Xu, Weijun,Reid, Robert C.,Fairlie, David P.
supporting information
p. 5956 - 5971
(2020/06/05)

Cobalt-catalyzed C[sbnd]H activation/C[sbnd]O formation: Synthesis of benzofuranones
Herein, C[sbnd]H activation/C[sbnd]O formation reaction using novel cobalt catalytic system is reported. This reaction was given benzofuranones in moderate to excellent yields at room-temperature under air reaction conditions. The introduced strategy is efficient and low-cost method to synthesized benzofuranones from α,α-disubstitution acetic acid.
Hajipour, Abdol R.,Khorsandi, Zahra
(2019/11/26)

Harnessing Applied Potential: Selective β-Hydrocarboxylation of Substituted Olefins
The construction of carboxylic acid compounds in a selective fashion from low value materials such as alkenes remains a long-standing challenge to synthetic chemists. In particular, β-addition to styrenes is underdeveloped. Herein we report a new electrosynthetic approach to the selective hydrocarboxylation of alkenes that overcomes the limitations of current transition metal and photochemical approaches. The reported method allows unprecedented direct access to carboxylic acids derived from β,β-trisubstituted alkenes, in a highly regioselective manner.
Alkayal, Anas,Buckley, Benjamin R.,Malkov, Andrei V.,Montanaro, Stephanie,Tabas, Volodymyr,Wright, Iain A.
supporting information

(2020/02/13)

ARYL-SUBSTITUTED ACETAMIDE AND PYRROLIDIN-2-ONE DERIVATIVES AND THEIR USE FOR THE TREATMENT OF SEIZURES
Aryl-substituted acetamide and pyrrolidin-2-one (γ-butyrolactam) derivatives have useful activity in the inhibition, prevention, or treatment of seizures. The derivatives may be useful in the treatment of epilepsy, including medically refractory epilepsy, and nerve agent poisoning.
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Paragraph 0055; 0058

(2019/06/09)

Palladium-catalyzed 2-pyridylmethyl-directed β-C(sp3)–H activation and cyclization of aliphatic amides with gem-dibromoolefins: A rapid access to γ-lactams
The direct Pd-catalyzed β-C(sp3)–H activation and cyclization of aliphatic amides bearing a removable 2-pyridylmethyl directing group with gem-dibromoolefins is described for the first time to construct a variety of γ-lactams. The resulting products with Z- and E-configurations can be easily separated and purified after the reaction, demonstrating the effectiveness and applicability of the method herein developed.
Zhou, Danni,Wang, Chunxia,Li, Mingliang,Long, Zheng,Lan, Jingbo
supporting information
p. 191 - 193
(2017/11/17)

Visible-Light-Driven External-Reductant-Free Cross-Electrophile Couplings of Tetraalkyl Ammonium Salts
Cross-electrophile couplings between two electrophiles are powerful and economic methods to generate C-C bonds in the presence of stoichiometric external reductants. Herein, we report a novel strategy to realize the first external-reductant-free cross-electrophile coupling via visible-light photoredox catalysis. A variety of tetraalkyl ammonium salts, bearing primary, secondary, and tertiary C-N bonds, undergo selective couplings with aldehydes/ketone and CO2. Notably, the in situ generated byproduct, trimethylamine, is efficiently utilized as the electron donor. Moreover, this protocol exhibits mild reaction conditions, low catalyst loading, broad substrate scope, good functional group tolerance, and facile scalability. Mechanistic studies indicate that benzyl radicals and anions might be generated as the key intermediates via photocatalysis, providing a new direction for cross-electrophile couplings.
Liao, Li-Li,Cao, Guang-Mei,Ye, Jian-Heng,Sun, Guo-Quan,Zhou, Wen-Jun,Gui, Yong-Yuan,Yan, Si-Shun,Shen, Guo,Yu, Da-Gang
p. 17338 - 17342
(2019/01/04)

Palladium(II)-Catalyzed C(sp2)-H Carbonylation of Sterically Hindered Amines with Carbon Monoxide
A palladium-catalyzed, amine-directed C(sp2)-H carbonylation of α,α-disubstituted benzylamine under 1 atm of CO for the facile synthesis of sterically hindered benzolactam has been developed. The key to success is the use of 2,2,6,6-tetramethyl-1-piperidinyloxy as the crucial sole oxidant. The synthetic utility of this transformation has been demonstrated by the first concise synthesis of the natural product spiropachysin-20-one.
Cheng, Xiu-Fen,Wang, Tao,Li, Yan,Wu, Yun,Sheng, Jie,Wang, Rui,Li, Chao,Bian, Kang-Jie,Wang, Xi-Sheng
supporting information
p. 6530 - 6533
(2018/10/20)

A Core–Shell-Structured Silver Nanowire/Nitrogen-Doped Carbon Catalyst for Enhanced and Multifunctional Electrofixation of CO2
Numerous catalysts have been successfully introduced for CO2 fixation in aqueous or organic systems. However, a single catalyst showing activity in both solvent types is still rare, to the best of our knowledge. We developed a core–shell-structured AgNW/NC700 composite using a Ag nanowire (NW) core encapsulated by a N-doped carbon (NC) shell at 700 °C. Through control experiments and density functional theory calculations, it was confirmed that Ag nanowires acted as the active sites for CO2 fixation and the uniformly coating of N-doped carbon created a CO2-rich environment around the Ag nanowires, which could significantly improve the catalytic activity of Ag nanowires for electrochemical CO2 fixation. Under mild conditions, up to 96 % faradaic efficiency of CO, 95 % yield of Ibuprofen and 92 % yield of propylene carbonate could be obtained in the electrochemical CO2 direct reduction, carboxylation and cycloaddition, respectively, using the same AgNWs/NC700 catalyst. These results might provide an alternative strategy for efficient electrochemical fixation of CO2.
Yang, Heng-Pan,Zhang, Han-Wen,Wu, Yu,Fan, Liang-Dong,Chai, Xiao-Yan,Zhang, Qian-Ling,Liu, Jian-Hong,He, Chuan-Xin
p. 3905 - 3910
(2018/09/27)

Platinum/nitrogen-doped carbon/carbon cloth: A bifunctional catalyst for the electrochemical reduction and carboxylation of CO2 with excellent efficiency
A novel Pt-NP@NCNF@CC composite was prepared by the electrospinning technique. It is a highly efficient and binder-free catalyst for the direct reduction and carboxylation of CO2 with halides. Formate with 91% Faradaic efficiency and 2-phenylpropionic acid with 99% yield could be obtained, respectively. Moreover, this catalyst has excellent stability and reusability.
Yang, Heng-Pan,Lin, Qing,Zhang, Han-Wen,Li, Guo-Dong,Fan, Liang-Dong,Chai, Xiao-Yan,Zhang, Qian-Ling,Liu, Jian-Hong,He, Chuan-Xin
supporting information
p. 4108 - 4111
(2018/04/27)

Nickel-catalysed direct alkylation of thiophenes via double C(sp3)-H/C(sp2)-H bond cleavage: The importance of KH2PO4
A Ni-catalyzed oxidative C-H/C-H cross-dehydrogenative coupling (CDC) reaction was developed for constructing various highly functionalized alkyl (aryl)-substituted thiophenes. This method employs thiophenes and aliphatic (aromatic) amides that contain an 8-aminoquinoline as a removable directing group in the presence of a silver oxidant. The approach enables the facile one-step synthesis of substituted thiophenes with high functional group compatibility via double C-H bond cleavage without affecting C-Br and C-I bonds. DFT calculations verify the importance of KH2PO4 as an additive for promoting C-H bond cleavage and support the involvement of a Ni(iii) species in the reaction.
Wang, Xie,Xie, Peipei,Qiu, Renhua,Zhu, Longzhi,Liu, Ting,Li, You,Iwasaki, Takanori,Au, Chak-Tong,Xu, Xinhua,Xia, Yuanzhi,Yin, Shuang-Feng,Kambe, Nobuaki
supporting information
p. 8316 - 8319
(2017/07/26)

Synthetic method of fexofenadine intermediate
The invention provides a synthetic method of a fexofenadine intermediate 2-[4-[4-[4-(hydroxybenzhydryl)-1-piperidyl]-butyryl]phenyl]-2- methylmethacrylate. The method comprises the following steps: methylation of phenylacetonitrile which is used as a raw material, basic hydrolysis, weinreb amidation reaction, Friedel-crafts reaction, acid hydrolysis, esterification and condensation. The method has the following advantages: raw materials and auxiliary materials are cheap and easily available; yield is high; cost is low; there is no meta-isomer; and the method is suitable for industrial production.
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Paragraph 0010; 0032; 0033; 0034; 0035; 0036

(2017/02/28)

Highly efficient hybrid cobalt-copper-aluminum layered double hydroxide/graphene nanocomposites as catalysts for the oxidation of alkylaromatics
The selective oxidation of alkylaromatics is of vital importance for the production of high-added-value raw materials. The development of highly efficient heterogeneous catalytic oxidation systems under mild conditions has become an attractive research area. In this work, hybrid Co-Cu-Al layered double hydroxide/graphene (CoCuAl-LDH/graphene) nanocomposites, which were assembled successfully by a one-step coprecipitation route without the use of any additional reducing agents, were used as highly efficient catalysts for the liquid-phase selective oxidation of ethylbenzene using tert-butyl hydroperoxide as the oxidant. A series of characterizations revealed that graphene could stabilize CoCuAl-LDH nanoplatelets effectively in the nanocomposites, and in turn, highly dispersed CoCuAl-LDH could prevent the aggregation of the graphene nanosheets. By fine-tuning the mass ratio of graphene to CoCuAl-LDH, such nanocomposites offered a tunable catalytic oxidation performance. In particular, the nanocomposite with the graphene/CoCuAl-LDH mass ratio of 0.4:1 exhibited a remarkable catalytic performance with a considerable conversion (96.8 %) and selectivity to acetophenone (>95.0 %), which was mainly attributed to the synergism between the active CoCuAl-LDH component and the graphene matrix in the unique hetero-nanostructure. Moreover, the as-assembled nanocomposite catalysts displayed good recyclability and were active for the selective oxidation of other alkylaromatics. Mega results for nanocomposites: The liquid-phase selective oxidation of alkylaromatics is conducted successfully on well-dispersed hybrid Co-Cu-Al layered double hydroxide/graphene nanocomposites, which show an excellent catalytic performance attributable to the synergy between the active Co-Cu-Al layered double hydroxide component and the graphene matrix in the unique hetero-nanostructure of the nanocomposites.
Xie, Renfeng,Fan, Guoli,Yang, Lan,Li, Feng
p. 363 - 371
(2016/02/05)

Nickel-catalyzed directed sulfenylation of sp2 and sp3 C-H bonds
Directed sulfenylation of both sp2 and sp3 C-H bonds was achieved through nickel catalyzed directed C-S bond formation, giving the desired product in good to excellent yield (up to 90%). Other metal cations, including Cu, Fe, Pd, Rh, Ru and Co, gave almost no reaction under identical conditions, which highlighted the unique reactivity of this Ni system.
Ye, Xiaohan,Petersen, Jeffrey L.,Shi, Xiaodong
supporting information
p. 7863 - 7866
(2015/05/13)

Palladium(II)-catalyzed directed trifluoromethylthiolation of unactivated C(sp3)-H bonds
The synthesis of trifluoromethylthiolated aliphatic acid derivatives by Pd-catalyzed C(sp3)-H bond functionalization was developed. Using a bidentate directing group, the direct and selective introduction of a SCF3 moiety was possible on a range of amides with remarkable selectivity for C(sp3)-centers with an electrophilic SCF3 source and pivalic acid as an additive. This work constitutes an example of the unactivated C(sp3)-SCF3 bond formation by C-H activation offering a new access to relevant molecules.
Xiong, Heng-Ying,Besset, Tatiana,Cahard, Dominique,Pannecoucke, Xavier
p. 4204 - 4212
(2015/05/05)

NOVEL PROCESS FOR THE PREPARATION OF 2-[4-(2-{4-[1-(2-ETHOXYETHYL)-1H-BENZIMIDAZOL-2-YL]-1-PIPERIDINYL}ETHYL) PHENYL]-2-METHYLPROPANOIC ACID
The present invention relates to novel process for the preparation of 2-[4-(2-{4-[l-(2- ethoxyethyl)-lH-benzimidazol-2-yl]-l-piperidinyl}ethyl)phenyl]-2-methylpropanoic acid represented by the following structural formula- 1. Formula- 1 The present invention also provides novel intermediate compounds useful for the preparation of compound of formula- 1.
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Page/Page column 22

(2014/12/12)

SPIRO-SUBSTITUTED OXINDOLE DERIVATIVES HAVING AMPK ACTIVITY
The present invention relates to compounds of formula (I), which have valuable pharmacological properties, in particular are activators of AMPK and which are therefore useful in the treatment of certain disorders that can be prevented or treated by activation of this receptor. The compounds are suitable for treatment and prevention of diseases which can be influenced by this receptor, such as metabolic diseases, in particular diabetes type 2.
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Page/Page column 113

(2015/01/07)

OLEFIN SUBSTITUTED OXINDOLES HAVING AMPK ACTIVITY
The present invention relates to compounds of formula (I), which have valuable pharmacological properties, in particular are activators of AMPK and which are therefore useful in the treatment of certain disorders that can be prevented or treated by activation of this receptor. The compounds are suitable for treatment and prevention of diseases which can be influenced by this receptor, such as metabolic diseases, in particular diabetes type 2.
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Page/Page column 107

(2015/01/07)

PREPARATION OF 2-(4-BROMOPHENYL)-2-METHYLPROPANOIC ACID
Selective bromination of 2-methyl-2-phenylpropanoic acid in aqueous medium is described to obtain pure 2-(4-bromophenyl)-2-methylpropanoic acid, which is a useful key intermediate in the process of manufacturing pure fexofenadine.
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Page/Page column 3

(2012/12/14)

Preparation of 2-(4-bromophenyl)-2-methylpropanoic acid
Selective bromination of 2-methyl-2-phenytpropanoic acid on aqueous medium is described to obtain pure 2-(4-bromophenyl)-2-methylpropanoic acid, which is a useful key intermediate in the process of manufacturing pure fexofenadine.
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Page/Page column 4; 6

(2013/02/27)

METAL-CATALYSED CARBONYLATION OF UNSATURATED COMPOUNDS
The invention provides a method for the hydroxycarbonylation, alkoxycarbonylation, aryloxycarbonylation or thiocarbonylation of an unsaturated molecule. The method includes a hydroxycarbonylation, alkoxycarbonylation, aryloxycarbonylationor thiocarbonylation reaction on the unsaturated molecule in which a complex including a ligand comprising a [n,n′]cyclophane comprising two non-fused monocyclic aromatic rings bridged by two linear and aliphatic linkages, in which each of the non-fused monocyclic aromatic rings is substituted with a phosphorus atom-containing substituent, is used to catalyse the reaction.
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Page/Page column 12-13

(2012/07/27)

METAL CATALYSED CARBONYLATION OF UNSATURATED COMPOUNDS
The invention provides a method for the hydroxycarbonylation, alkoxycarbonylation, aryloxycarbonylation or thiocarbonylation of an unsaturated molecule comprising effecting a hydroxycarbonylation, alkoxycarbonylation, aryloxycarbonylation or thiocarbonylation reaction on the unsaturated molecule in which a complex comprising a ligand comprising a [n,n']cyclophane comprising two non-fused monocyclic aromatic rings bridged by two linear and aliphatic linkages, in which each of the non-fused monocyclic aromatic rings is substituted with a phosphorus atom-containing substituent, is used to catalyse the hydroxycarbonylation, alkoxycarbonylation, aryloxycarbonylation or thiocarbonylation reaction.
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Page/Page column 29-30

(2011/04/18)

Understanding the differential performance of Rh2(esp) 2 as a catalyst for C-H amination
(Chemical Equation Presented) Catalytic amination of saturated C-H bondsis performed efficiently with the use of Rh2(esp)2. Efforts to identify pathways for catalyst degradation and/or arrest have revealed a singleelectron oxidation event that gives rise to a red-colored, mixed-valence dimer, [Rh2(esp)2]+. This species is fortuitously reduced by carboxylic acid, a byproductgenerated in the reaction cycle with each turnover of the diacyloxyiodi ne oxidant. These findings have led to the conclusion that the high performance of Rh2(esp)2 is due in part to the superior kinetic stability of its one-electron oxidized form relative to other dimeric Rh complexes.
Zalatan, David N.,Bois, J. Du
supporting information; experimental part
p. 7558 - 7559
(2009/10/17)

Metalation of toluene and cumene with alkali metal-crown ether complexes
Metalation of toluene and isopropylbenzene with alkali metal-crown ether complexes led to the corresponding α-metalated alkylbenzenes. Treatment of the latter in succession with solid carbon dioxide, water, and hydrochloric acid gave carboxylic or dicarboxylic acids in 65-78% yield. Metalation of isopropylbenzene with sodium or potassium crown ether complexes above 90°C was accompanied by cleavage of the polyether ring with formation of organometallic compounds which then reacted with isopropylbenzene to produce 2-sodio(potassio)-2-phenylpropane and open-chain oligoether.
Shabanov,Seidov,Gasanova,Kakhramanova,Gasanova
experimental part
p. 26 - 29
(2009/06/28)

Hepatitis C NS5B polymerase inhibitors: 4,4-Dialkyl-1-hydroxy-3-oxo-3,4-dihydronaphthalene-3-yl benzothiadiazine derivatives
4,4-Dialkyl-1-hydroxy-3-oxo-3.4-dihydronaphthalene-3-yl benzothiadiazine derivatives were synthesized and evaluated as inhibitors of genotypes 1a and 1b HCV NS5B polymerase. A number of these compounds exhibited potent activity against genotypes 1a and 1b HCV polymerase in both enzymatic and cell culture activities. A representative compound also showed favorable pharmacokinetics in the rat.
Hutchinson, Douglas K.,Rosenberg, Teresa,Klein, Larry L.,Bosse, Todd D.,Larson, Daniel P.,He, Wenping,Jiang, Wen W.,Kati, Warren M.,Kohlbrenner, William E.,Liu, Yaya,Masse, Sherie V.,Middleton, Tim,Molla, Akhteruzzaman,Montgomery, Debra A.,Beno, David W.A.,Stewart, Kent D.,Stoll, Vincent S.,Kempf, Dale J.
scheme or table
p. 3887 - 3890
(2009/04/07)

A novel synthetic route to 2-arylalkanoic acids by a ruthenium-catalyzed chemoselective oxidation of furan rings
An efficient two-step synthesis of 2-arylalkanoic acids from 1-arylalkanols is described. Firstly, 1-arylalkylfuran derivatives were synthesized in high yields by the metal triflate catalyzed Friedel-Crafts alkylation of 2-methylfuran with 1-arylalkanols without employing anhydrous conditions. The chemoselective oxidation of the furan ring in 1-arylalkylfurans to carboxylic acid was then investigated. In a solvent system of hexane-EtOAc/H2O (1:3:4), the furan ring was selectively oxidized with 7 equivalents of NaIO 4 by using 0.5 mol% RuCl3 as catalyst to give 2-arylalkanoic acids in good yields. The selectivity of ruthenium oxidation was controlled by the solvent ratio of hexane-EtOAc. Georg Thieme Verlag Stuttgart.
Noji, Masahiro,Sunahara, Haruka,Tsuchiya, Ken-Ichi,Mukai, Toru,Komasaka, Ayako,Ishii, Keitaro
experimental part
p. 3835 - 3845
(2009/07/04)

Anti-infective agents
Compounds having the formula are hepatitis C (HCV) polymerase inhibitors. Also disclosed are a composition and method for inhibiting hepatitis C (HCV) polymerase, processes for making the compounds, and synthetic intermediates employed in the processes.
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Page/Page column 71

(2008/06/13)

ANTI-INFECTIVE AGENTS
Compounds having the formula (I) are hepatitis C (HCV) polymerase inhibitors. Also disclosed are a composition and method for inhibiting hepatitis C (HCV) polymerase, processes for making the compounds, and synthetic intermediates employed in the processes.
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Page/Page column 141

(2010/02/11)

FEXOFENADINE POLYMORPHS AND PROCESSES OF PREPARING THE SAME
Anhydrous crystalline fexofenadine hydrochloride Form C, crystalline fexofenadine acetate monohydrate Form D, crystalline fexofenadine acetate dihydrate Form E and crystalline fexofenadine free base monohydrate Form F, processes of preparing the same, pharmaceutical compositions thereof, therapeutic uses thereof and methods of treatment therewith.
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Page/Page column 23

(2008/06/13)

Alkali metal ion controlled product selectivity during photorearrangements of 1-naphthyl phenyl acylates and dibenzyl ketones within zeolites
Photochemical behaviors of 1-naphthyl phenyl acylates and dibenzyl ketones included in zeolites have been compared. 1-Naphthyl phenyl acylates while in solution produce eight photoproducts; within NaY it gives a single product. The selectivity is attributed to the restriction brought on the mobility of the primary radical pair by the alkali metal ions present in zeolites. Photochemistry of dibenzyl ketones within NaY reveals that the intersystem crossing in caged radical pairs could be influenced by the heavy alkali metal ions. Structures of complexes among Li+ ion and the guest 1-naphthyl phenyl acetates and dibenzyl ketone computed at the B3LYP level have been useful to understand the origin of the observed product selectivity within zeolites.
Warrier,Kaanumalle, Lakshmi S.,Ramamurthy
p. 620 - 631
(2007/10/03)

Reductive lithiation of alkyl phenyl sulfides in diethyl ether. A ready access to α,α-dialkylbenzyllithiums
Diethyl ether is a convenient solvent for the conversion of benzylic phenyl sulfides to the corresponding organolithiums by an uncatalyzed reductive metalation, while catalysis by naphthalene is required to achieve the same reaction for alkyl phenyl sulfides. The addition of magnesium 2-ethoxyethoxide to solutions of unstable alkyllithiums prepared in this way provides storable reagents.
Screttas, Constantinos G.,Heropoulos, Georgios A.,Micha-Screttas, Maria,Steele, Barry R.,Catsoulacos, Dimitrios P.
p. 5633 - 5635
(2007/10/03)

Process for the preparation of α,α- dimethylphenylacetic acid from α,α-dimethylbenzyl cyanide under normal pressure
A process for obtaining α,α-dimethylphenylacetic acid wherein α,αdimethylbenzyl cyanide is reacted in the presence of sodium hydroxide, water and a C4- and/or C5-alcohol at temperatures above about 100° C. and the α,α-dimethylphenylacetic acid is obtained by acidification.
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(2008/06/13)

Unexpected formation of 3,3a,4,7a-tetrahydrobenzofuran-2,5-dione as well as arene carboxylic acids upon formal double exo nucleophilic addition of R1R2C-COO- to anisolechromium tricarbonyl complexes
Bis(trimethylsily)ketene acetals of the general structure 2 (R1 = H,Me,R2 = Me,Et,Pr(i),CMe = CH2) react at -78°C in the presence of Bu(t)OK with a series of arenechromium tricarbonyl complexes 3 to give as expected, after oxidation with I2 followed by silica gel chromatography, arylcarboxylic acids 7. In the case of anisolechromium tricarbonyl 8, besides the m-methoxyarylcarboxylic acids, tetrahydrobenzofuran-2,5-diones 11, are formed as the result of a double nucleophilic addition.
Bellassoued, Moncef,Chelain, Evelyne,Collot, Jerome,Rudler, Henri,Vaissermann, Jacqueline
p. 187 - 188
(2007/10/03)

A new synthesis of carboxyterfenadine (fexofenadine) and its bioisosteric tetrazole analogs
A new synthesis of carboxyterfenadine (4), based on the conversion of a α-halo-alkylarylketone into the corresponding substituted 2-arylalkanoic ester, is described. The enantioselective synthesis of its two bioisosteric tetrazole analogs together with preliminary biological results are reported. Copyright (C) 1999 Elsevier Science S.A.
Di Giacomo, Barbara,Coletta, Donato,Natalini, Benedetto,Ni, Ming-Hong,Pellicciari, Roberto
p. 600 - 610
(2007/10/03)

Carbonylation of vinyl aromatics: Convenient regioselective synthesis of 2-arylpropanoic acids
(equation presented) Various substituted and nonsubstituted 2-arylpropanoic acids have been synthesized in high turnovers with high regioselectivity by palladium-catalyzed carbonylation of vinyl aromatics. Both terminal and internal olefins are carbonylated, though hindered olefins are less reactive. In all the cases high yields and high selectivity are observed. Olefins with electron-withdrawing para substituents gave the highest regioselectivity in the formation of the corresponding 2-arylpropanoic acids.
Seayad,Jayasree,Chaudhari
p. 459 - 461
(2008/02/11)

Synthesis of substituted benzyl 2-methyl-2-phenylpropyl ethers and their moth-proofing activity on wool against larvae of Anthrenus fasciatus
Synthesis of new moth-proofing agents is necessary to overcome the damage caused by clothes moths and carpet beetles to hosiery and upholstery. In the present paper substituted benzyl 2-methyl-2-phenylpropyl ethers were synthesised and evaluated for moth-proofing activity. Two compounds were found to provide protection against larvae of Anthrenus fasciatus at levels of 1.0 and 10 g kg-1 respectively. The introduction of a methyl group in the para position of the benzene ring attached to C2 of the 2-methylpropyl chain (ring A) increased moth-proofing activity. The introduction of a phenoxy ring at the meta position of the benzyl nucleus (ring B) also increased activity, while the presence of a nitro group on the benzyl nucleus (ring B) decreased activity.
Acharya,Joshi
p. 850 - 856
(2007/10/03)

Benzodiazepine derivatives useful as CCK-receptor antagonists
This invention relates to benzodiazepine derivatives which are useful as drugs exhibiting antagonism at the gastrin and/or CCK-B receptor, and to their production.
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(2008/06/13)

Antihistaminic compounds, process for their preparation and pharmaceutical compositions containing them
The present invention relates to terfenadine derivatives of formula where R?, which is in position 1 or 2 of the tetrazole ring, stands for H, or a linear or branched alkyl group containing from 1 to 6 carbon atoms; R? and R?, different from one another, are selected between H and OH, and their pharmaceutically acceptable salts.
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(2008/06/13)

Spectroscopy and photochemistry of phenylacetic acid esters and related substrates. The stereoelectronic dependence of the aryl/carboxyl bichromophore interaction
The 254-nm-initiated Norrish Type II photofragmentation of the ethoxyethyl esters of a series of phenylacetic acids (1b-4b) has been studied in order to further elaborate the aryl/ester interaction that is photochemically and photophysically evident in these systems. The ethoxyethyl ester of benzonorbornene-1-carboxylic acid (5) has also been prepared and studied, as has a rigid tricyclic lactone (6) which places the chromophores in an optimal stereoelectronic relationship for interaction. The experimental work is accompanied by Hartree-Fock (HF), Natural Bond Orbital (NBO), and Configuration Interaction with Single Excitations (CIS) calculations on the methyl esters of phenylacetic acid (1a) and α-methoxyphenylacetic acid (4a). The calculations confirm extensive through-space (TS) and through-bond (TB) interactions between the aryl and ester π* orbitals but fail to provide conformational or electronic arguments to explain the unusually high reactivity of the α-methoxy series.
Kasper,Nash,Morrison
p. 2792 - 2798
(2007/10/02)

Thermolysis of Pentasubstituted 3-Hydroxy-1,2-dioxolanes
A series of pentasubstituted 3-hydroxy-1,2-dioxolanes, 1 a-e, was synthesized by oxygen trapping of β-keto radicals formed during α-azo hydroperoxide decomposition.Thermolysis of the pentasubstituted 3-hydroxy-1,2-dioxolanes (hemiperketals) in benzene proceeded cleanly and yielded pairs of ketones and carboxylic acids.Two of the hemiperketals yielded only one pair of products while the others produced two sets of products.One of each pair of fragmentation products had undergone skeletal rearrangement.Only methyl migrations were observed when in competition with phenyl groups from the same position.The activation parameter data for 1d = 24.3 kcal/mol, ΔS = -8.4 eu, ΔG = 27.1 kcal/mol, k60 deg = 3.1 * 10-5 s-1> were consisteat with O-O bond scission as the rate-determining-step.A likely mechanism for this thermolysis is initial peroxy bond homolysis to the 1,5-oxygen diradical followed by β-scissions with rearrangments.
Baumstark, A. L.,Vasquez, Pedro C.
p. 1781 - 1783
(2007/10/02)

Pyridylthio-acylanilide herbicides
Novel herbicidally active pyridylthio-acylanilides of the formula STR1 in which R1, R2 and R3, independently of one another, represent hydrogen, halogen, cyano or trifluoromethyl or alkyl, alkoxy and alkylthio having 1 to 4 carbon atoms in each case, R4 represents halogen, methyl or methoxy, n represents a number 0, 1 or 2, z represents the group (Ia) STR2 or the group (Ib) STR3 where X represents oxygen, sulphur, an N--R10 or N--O--R11 group, or X and Rg tpgether represent the STR4 radical, and the other radicals can have various meanings. Intermediates of the formulae STR5 are also new.
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(2008/06/13)

Silver ion induced reactions of α-haloimines
The silver ion induced reactions of α-haloimines are markedly different from similar reactions with the corresponding α-haloketones. The various reactions of α-haloimines, including α-alkoxylation 1,2-dehydrohalogenation, rearrangement via α-alkoxyaziridines, Favorskii-rearrangement and Wagner Meerwein rearrangement, are compared and evaluated with silver-induced reactions of α-haloketones The silver ion assisted reactions of α-haloimines are best interpreted in terms of the intermediacy c α-imidoylcarbenium ions or pseudo-α-imidoylcarbenium ions.
De Kimpe, Norbert,Stevens, Christian
p. 6753 - 6770
(2007/10/02)

Facile Cleavage of Bibenzyls by Cs-K-Na Alloy Leading to the Formation of Benzyl Carbanions
Facile cleavage of twelve substituted bibenzyls (1-12) with Cs-K-Na alloy at -75 deg C leading to the formation of benzyl carbanions has been studied.
Sengupta, Dibyendu,Grovenstein, E.
p. 185 - 186
(2007/10/02)

PHOTO-OXYGENATION OF ALKYLBENZENES BY A PLATINUM CATALYTIC SYSTEM
Alkylbenzenes are photo-oxygenated under air bubbling at room temperature, in the presence of a PtN2S2 complex as catalyst precursor.
Monaci, Anna
p. 339 - 340
(2007/10/02)

Synthesis of 2-Arylalkanoic Acids: Zinc Bromide-Assisted Methanolysis of α-Bromoalkyl Aryl Ketones
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Giordano, Claudio,Castaldi, Graziano,Uggeri, Fulvio,Gurzoni, Francesco
p. 436 - 437
(2007/10/02)

Carbanions. 23. Cleavage of 1,2-Diphenylethane and Derivatives by Cs-K-Na Alloy. Cometitive Rates of Bond Scission
The following hydrocarbons are cleaved at a C-C bond to allylic and or/benzylic cesium compounds within 2 h by Cs-K-Na alloy in THF at -75 deg C: meso-2,3-diphenylbutane, 2,3-dimethyl-2,3-diphenylbutane, 1,2,2-triphenylpropane, 4-phenyl-1-butene, bibenzyl, and eight o-,m-, or p-methyl derivatives of bibenzyl.Under the same conditions 2-methyl- and 3-methyl-4-phenyl-1-butene were partially cleaved, 4,4'-dimethylbibenzyl was only slightly cleaved, and 9,10-dihydrophenanthrene was not detectably cleaved, while 10,11-dihydro-5H-dibenzocycloheptene underwent alternative C-H bond cleavage.Under the present reaction conditions 4,4'-dimethylbibenzyl and 9,10-dihydrophenanthrene were converted largely to dianions.It is suggested that all of the compounds undergoing cleavage are converted to dianions prior to cleavage.From competitive experiments the rates of reductive cleavage of most of these hydrocarbons relative to bibenzyl have been measured at -75 deg C.The relative rates of cleavage of m- and p-methylderivatives of bibenzyl may be correlated with the relative equilibrium acidities of toluene, m-xylene, and p-xylene in a modified Hammett relationship.Cleavages of benzylic C-C bonds are believed to occur by way of a preferred transition-state geometry,7, which permits the ?* orbital of the bond undergoing cleavage to interact with the HOMO's of both aromatic rings.Compounds that cannot attain this transition-state geometry are cleaved slowly if at all.The variable effect upon reaction rate of methyl groups near the bond undergoing cleavage are discussed in terms of ground-state and transition-state atrain, solvation, and polarizability of methyl groups.According to labeling experiments (o-methylbenzyl)cesium undergoes ready intramolecular sigmatropic migration of hydrogen from the methyl group to the methylene group when warmed from -75 deg C to near room temperature.
Grovenstein, Erling,Bhatti, Amjad M.,Quest, Dean E.,Sengupta, Dibyendu,VanDerveer, Don
p. 6290 - 6299
(2007/10/02)

New Methods and Reagents in Organic Synthesis. 34. Diphenyl Phosphorazidate (DPPA) as a 1,3-Dipole. A Simple, Efficient Conversion of Alkyl Phenyl Ketones to 2-Phenylalkanoic Acids
Propiophenone (11) was conveniently converted to its enamines 12a-c using boron trifluoride etherate as a catalyst.Reaction of diphenyl phosphorazidate (DPPA) with the enamines 12a-c efficiently afforded the N-phosphorylated amidines 14a-c by the 1,3-dipolar cycloaddition of DPPA to the enamine double bond, followed by the evolution of nitrogen from the intermediate triazoline 13, and 1,2-migration of the phenyl group. 1,3-Dipolar elimination products 15a-c were also formed, though in very low yields.Some chemical properties of the N-phosphorylated amidine 14a, as well as the 1,3-dipolar character of DPPA, were investigated.By the same reaction sequences (enamine formation followed by the 1,3-dipolar cycloaddition of DPPA), some alkyl phenyl ketones 29a-c were conveniently converted to the N-phosphorylated amidines 31a, 31b, and 27 via the enamines 30a-c.However , in the case of acetophenone and its derivatives 33a-c, these reaction sequences proceeded sluggishly.Alkaline hydrolysis of the N-phosphorylated amidines 14a, 31a, 31b and 27 with potassium hydroxide afforded 2-phenylalkanoic acids 25 and 32a-c, respectively, in excellent yields.The overall three-step process of successive treatment of alkyl phenyl ketones (alkylmethyl) with pyrrolidine, DPPA, and potassium hydroxide may provide a new general method for the efficient conversion of alkyl aryl ketones to 2-arylalkanoic acids.Keywords - enamine; diphenyl phosphorazidate; boron trifluoride etherate; 1,3-dipolar cycloaddition; 1,2-migration; N-phosphorylated amidine; alkaline hydrolysis; alkyl aryl ketone; 2-arylalkanoic acid
Kawai, Nobutaka,Shioiri, Takayuki
p. 2564 - 2573
(2007/10/02)

1,8,17,24-Tetraoxa(2,6)naphthalenophane-3,5,19,21-tetrayne-10,13-dicarboxylic Acid Derivatives, Novel Complexors of Aromatic Guests
Synthesis and complexation behavior of the title molecules are described.Study of aromatic solvent induced shifts of these molecules support the contention that their large cavity can accomodate aromatic rings.The behavior of acid 1a in water suggests that this effect enhanced in aqueous medium, as is expected for formation of hydrophobic inclusion complexes.In contrast to the rigid naphthalenophanes (1), their saturated derivatives (7) exist in a collapsed conformation and do not incorporate aromatic guests.
Jarvi, Esa T.,Whitlock, Howard W.
p. 7196 - 7204
(2007/10/02)