- Facile transformation of benzocyclobutenones into 2,3-benzodiazepines via 4π-8π tandem electrocyclic reactions involving net insertion of diazomethylene compounds
-
Efficient transformations of benzocyclobutenones into 2,3-benzodiazepines by a formal insertion of diazomethylene compounds are described. This sequential process includes nucleophilic addition of diazomethylene anion, oxy-anion accelerated o-quinodimethane formation by an electrocyclic ring-opening reaction, and 8π-electrocyclization in one-pot under remarkably mild conditions. Intermediary oxy-anion plays an important role for the efficient transformations. Copyright
- Matsuya, Yuji,Ohsawa, Noriko,Nemoto, Hideo
-
-
Read Online
- Kinetics-Driven Drug Design Strategy for Next-Generation Acetylcholinesterase Inhibitors to Clinical Candidate
-
The acetylcholinesterase (AChE) inhibitors remain key therapeutic drugs for the treatment of Alzheimer's disease (AD). However, the low-safety window limits their maximum therapeutic benefits. Here, a novel kinetics-driven drug design strategy was employed to discover new-generation AChE inhibitors that possess a longer drug-target residence time and exhibit a larger safety window. After detailed investigations, compound 12 was identified as a highly potent, highly selective, orally bioavailable, and brain preferentially distributed AChE inhibitor. Moreover, it significantly ameliorated cognitive impairments in different mouse models with a lower effective dose than donepezil. The X-ray structure of the cocrystal complex provided a precise binding mode between 12 and AChE. Besides, the data from the phase I trials demonstrated that 12 had good safety, tolerance, and pharmacokinetic profiles at all preset doses in healthy volunteers, providing a solid basis for its further investigation in phase II trials for the treatment of AD.
- Zhou, Yu,Fu, Yan,Yin, Wanchao,Li, Jian,Wang, Wei,Bai, Fang,Xu, Shengtao,Gong, Qi,Peng, Tao,Hong, Yu,Zhang, Dong,Zhang, Dan,Liu, Qiufeng,Xu, Yechun,Xu, H. Eric,Zhang, Haiyan,Jiang, Hualiang,Liu, Hong
-
p. 1844 - 1855
(2021/03/01)
-
- Electrochemical Difunctionalization of Styrenes via Chemoselective Oxo-Azidation or Oxo-Hydroxyphthalimidation
-
Atom- and step-economic oxo-azidation and oxo-hydroxyphthalimidation of styrenes have been developed under mild electrolytic conditions, respectively. Various valuable alpha-azido or hydroxyphthalimide aromatic ketones were synthesized efficiently from readily available styrenes, azides, and N-hydroxyphthalimides. Mechanism studies show that two different pathways involved in these two transformations.
- Jiang, Haobin,Wang, Feng,Ye, Zenghui,Zhang, Fengzhi,Zhu, Rongjin
-
supporting information
p. 8240 - 8245
(2021/11/17)
-
- Development of a Flow Photochemical Aerobic Oxidation of Benzylic C-H Bonds
-
A continuous mesofluidic process has been developed for benzylic C-H oxidation with moderate to good yields using a photocatalyst (riboflavin tetraacetate, RFT) activated by a UV lamp and an iron additive [Fe(ClO4)2] via incorporation of singlet oxygen (1O2) for the direct formation of oxidized C=O or CH-OH compounds.
- Lesieur, Mathieu,Genicot, Christophe,Pasau, Patrick
-
supporting information
p. 1987 - 1990
(2018/04/16)
-
- BENZOCYCLOOCTENE-BASED AND INDENE-BASED ANTICANCER AGENTS
-
Benzocyclooctene (fused 6,8 ring system) analogues and corresponding indene (fused 6,5 ring system) analogues function as inhibitors of tubulin polymerization. The compounds are useful as anticancer agents in a new therapeutic approach for cancer treatment utilizing small-molecule inhibitors of tubulin polymerization that also act as vascular disrupting agents (VDAs).
- -
-
Paragraph 0095
(2018/02/27)
-
- Synthesis of diaryl ketones through oxidative cleavage of the C-C double bonds in N -Sulfonyl enamides
-
An oxidative cleavage of a C-C double bond is developed from the photochemical [2+2]-cycloaddition of diaryl N-tosyl enamides, aryl heteroaryl N-tosyl enamides, and N-tosyl cyclic enamides with singlet molecular oxygen, followed by a ring-opening reaction mediated by Cs2CO3 under air and sunlight without the use of photosesitizer, producing symmetrical and unsymmetrical diaryl, heterodiaryl, and cyclic ketones in good to excellent yields. Moreover, the oxidative cleavage of C-C triple bonds from 1-alkynes is demonstrated for the synthesis of symmetrical and unsymmetrical ketones from the Cu-catalyzed [3+2]-cycloaddition, Rh-catalyzed alkoxyarylation, photooxygenation, and ring-opening reaction in one-pot. Because the synthesis of the symmetrical and unsymmetrical diaryl and/or heterodiaryl ketones bearing an electron-donating group is not easy, the present method is notable.
- Kim, Hyunseok,Park, Sangjune,Baek, Yonghyeon,Um, Kyusik,Han, Gi Uk,Jeon, Da-Hye,Han, Sang Hoon,Lee, Phil Ho
-
p. 3486 - 3496
(2018/04/14)
-
- Benzylic C(sp3)-H Functionalization for C-N and C-O Bond Formation via Visible Light Photoredox Catalysis
-
A visible light mediated highly selective benzylic C-H bond functionalization for intermolecular C-N and C-O bond formation is reported. This cross-dehydrogenative coupling reaction demonstrates a straightforward protocol for incorporating the heteroaromatics to the benzylic position. Benzylic oxidation of various alkyl aryls to corresponding carbonyl compounds has also been reported.
- Pandey, Ganesh,Laha, Ramkrishna,Singh, Deepak
-
p. 7161 - 7171
(2016/08/30)
-
- Synthesis and biological evaluation of benzocyclooctene-based and indene-based anticancer agents that function as inhibitors of tubulin polymerization
-
The natural products colchicine and combretastatin A-4 (CA4) have been inspirational for the design and synthesis of structurally related analogues and spin-off compounds as inhibitors of tubulin polymerization. The discovery that a water-soluble phosphate prodrug salt of CA4 (referred to as CA4P) is capable of imparting profound and selective damage to tumor-associated blood vessels paved the way for the development of a new therapeutic approach for cancer treatment utilizing small-molecule inhibitors of tubulin polymerization that also act as vascular disrupting agents (VDAs). Combination of salient structural features associated with colchicine and CA4 led to the design and synthesis of a variety of fused aryl-cycloalkyl and aryl-heterocyclic compounds that function as inhibitors of tubulin polymerization. Prominent among these compounds is a benzosuberene analogue (referred to as KGP18), which demonstrates sub-nM cytotoxicity against human cancer cell lines and functions (when administered as a water-soluble prodrug salt) as a VDA in mouse models. Structure activity relationship considerations led to the evaluation of benzocyclooctyl [6,8 fused] and indene [6,5 fused] ring systems. Four benzocyclooctene and four indene analogues were prepared and evaluated biologically. Three of the benzocyclooctene analogues were active as inhibitors of tubulin polymerization (IC50 50 = 11 μM) with reduced potency. The most potent inhibitor of tubulin polymerization from this group was benzocyclooctene analogue 23, and it was converted to its water-soluble prodrug salt 24 to assess its potential as a VDA. Preliminary in vivo studies, which utilized the MCF7-luc-GFP-mCherry breast tumor in a SCID mouse model, demonstrated that treatment with 24 (120 mg kg?1) resulted in significant vascular shutdown, as evidenced by bioluminescence imaging at 4 h post administration, and that the effect continued at both 24 and 48 h. Contemporaneous studies with CA4P, a clinically relevant VDA, were carried out as a positive control.
- Herdman, Christine A.,Strecker, Tracy E.,Tanpure, Rajendra P.,Chen, Zhi,Winters, Alex,Gerberich, Jeni,Liu, Li,Hamel, Ernest,Mason, Ralph P.,Chaplin, David J.,Trawick, Mary Lynn,Pinney, Kevin G.
-
supporting information
p. 2418 - 2427
(2016/12/18)
-
- SUBSTITUTED HETEROCYCLIC DERIVATIVES AS GPR AGONISTS AND USES THEREOF
-
The present invention generally relates to substituted heterocyclic derivatives (the compounds of Formula (I)), processes for their preparation, pharmaceutical compositions containing said compounds, their use as G-protein coupled receptor (GPR) agonists, particularly as GPR40 agonists and methods of using these compounds in the treatment of GPR40 mediated diseases or conditions such as Type 2 diabetes, obesity, dyslipidemia, hyperlipidemia, hypercholesterolemia, and hypertriglyceridemia.
- -
-
Page/Page column 130
(2015/03/16)
-
- Synthesis and antitumor activity evaluation of 2-arylisoquinoline-1,3(2H, 4H)-diones in vitro and in vivo
-
Six 2-(2-acylaminobenzothiazol-6-yl)isoquinoline-1,3(2H,4H)-diones (1a-1f) and five 2-arylisoquinoline-1,3(2H,4H)-diones (1g-1k) were synthesized by refluxing homophthalic anhydrides with 2-acylaminobenzothiazolyl-6-amine or substituted aniline in glacial acetic acid. The cytotoxic activities of 1a-1k were evaluated via MTT method against A431, A549, and PC3. Compound 1b relatively displayed a higher cytotoxic activity than the others. The antitumor effect of 1b were evaluated in established nude mice PANC-1 xenograft model. The results suggest that compound 1b could potentially inhibit tumor growth.
- Kang, Bo-Rui,Wang, Juan,Li, Huan,Li, Yan,Mei, Qi-Bing,Zhang, San-Qi
-
p. 1340 - 1349
(2014/03/21)
-
- Efficient synthesis and resolution of novel 2-(hydroxymethyl)-7,8-dihydro- 1H-indeno[5,4-b] furan-6(2H)-one by lipase Pseudomonas cepacia
-
Lipase Pseudomonas cepacia catalyzed acylation of (±)-2- (hydroxymethyl)-7,8-dihydro-1H-indeno[5,4-b] furan-6(2H)-one using vinyl acetate as the acyl donor in acetone gave (-)-(R)-2-acetoxy-2-(methyl)-7,8-dihydro-1H- indeno[5,4-b] furan-6(2H)-one and (+)-(S)-2-(hydroxymethyl)-7,8-dihydro-1H- indeno[5,4-b] furan-6(2H)-one with high enantiomeric excess. Enantiomerically pure 2-(hydroxymethyl)-7,8-dihydro-1H-indeno[5,4-b] furan-6(2H)-one are useful intermediates for the preparation of Ramelteon, an FDA approved drug for the treatment of insomnia.
- Nagarapu, Lingaiah,Vulupala, Hanmanth Reddy,Bantu, Rajashaker,Sajja, Yashodakrishna,Nanubolu, Jagadeesh Babu
-
p. 578 - 582
(2014/05/06)
-
- POTENT SMALL MOLECULE INHIBITORS OF AUTOPHAGY, AND METHODS OF USE THEREOF
-
Certain aspects of the invention relate to small molecule autophagy inhibitors, and their use for treatment and prevention of cancers and acute pancreatitis. Medicinal chemistry studies led to small molecular autophagy inhibitors with improved potency and selectivity.
- -
-
Page/Page column 70; 71
(2014/09/29)
-
- Non-conventional methodologies in the synthesis of 1-indanones
-
1-Indanones have been successfully prepared by means of three different non-conventional techniques, namely microwaves, high-intensity ultrasound and a Q-tube reactor. A library of differently substituted 1-indanones has been prepared via one-pot intramolecular Friedel-Crafts acylation and their efficiency and "greenness" have been compared.
- Oliverio, Manuela,Nardi, Monica,Costanzo, Paola,Cariati, Luca,Cravotto, Giancarlo,Giofre, Salvatore Vincenzo,Procopio, Antonio
-
p. 5599 - 5610
(2014/06/10)
-
- AMINOINDANE DERIVATIVES, PHARMACEUTICAL COMPOSITIONS CONTAINING THEM, AND THEIR USE IN THERAPY
-
The present invention relates to aminoindane derivatives of the formula (I) or a physiologically tolerated salt thereof. The invention relates to pharmaceutical compositions comprising such aminoindane derivatives, and the use of such aminoindane derivatives for therapeutic purposes. The aminoindane derivatives are GlyT1 inhibitors.
- -
-
Page/Page column 95-96
(2012/03/08)
-
- α-Aryl-substituted allenamides in an imino-nazarov cyclization cascade catalyzed by Au(I)
-
An imino-Nazarov cyclization using α-aryl-substituted allenamides is described. This gold(I)-catalyzed cascade is efficient and regioselective in constructing a diverse array of synthetically useful aromatic-ring fused cyclopentenamides. The success in this transformation represents a solution to the challenge in establishing an imino-Nazarov cyclization process.
- Ma, Zhi-Xiong,He, Shuzhong,Song, Wangze,Hsung, Richard P.
-
p. 5736 - 5739
(2013/01/15)
-
- Synthesis and evaluation of dimeric 1,2,3,4-Tetrahydro-naphthalenylamine and Indan-1-ylamine derivatives with mast cell-stabilising and anti-allergic activity
-
In a continuation of our studies into 4-Amino-3,4-dihydro-2H-naphthalen-1-ones as novel modulators of allergic and inflammatory phenomena, we have extended our work to include dimeric analogues. Of these derivatives, the most promising activity was seen with tertiary amine 58a, which exhibited potent mast cell-stabilising activity in vitro against a variety of stimuli and also in vivo against passive cutaneous anaphylaxis.
- Barlow, James W.,Walsh, John J.
-
scheme or table
p. 25 - 37
(2010/03/04)
-
- Synthesis of 1-indanones via intramolecular cyclodehydration of 3-arylpropionic acids catalyzed by heteropoly acid as heterogeneous catalyst
-
Intramolecular cyclodehydration of 3-arylpropionic acids catalyzed by heteropoly acids was investigated for the first time. Several 3-arylpropionic acids were refluxed and dehydrated in chlorobenzene in the presence of 0.2 equivalent of heteropoly acids, and 1-indanones were obtained in good yield. At the same time, intermolecular Friedel-Crafts acylation were observed in this experiment. Copyright Taylor & Francis Group, LLC.
- Lan, Kun,Shan, Zi-Xing
-
p. 2171 - 2177
(2008/02/05)
-
- Ruthenium-catalyzed cyclization of 2-alkyl-1-ethynylbenzenes via a 1,5-hydrogen shift of ruthenium-vinylidene intermediates
-
(Chemical Equation Presented) Catalytic cyclization of 2-alkyl-1- ethynylbenzene derivatives was implemented by TpRuPPh3(CH 3CN)2PF6 (10 mol %) in hot toluene (105 °C, 36-100 h) to form 1-substituted-1H-indene and 1-indanone products; such cyclizations proceeded more efficiently for substrates bearing electron-rich benzenes. We propose that the cyclization mechanism involves a 1,5-hydrogen shift of initial metal-vinylidene intermediate.
- Odedra, Arjan,Datta, Swarup,Liu, Rai-Shung
-
p. 3289 - 3292
(2008/02/03)
-
- TiO2-sensitised photo-oxidation mechanism of indane and some of its hetero-analogues in deaerated CH3CN
-
A mechanistic study, principally based on product analysis, relative to the TiO2-photosensitized oxidation of indane and some of its hetero-analogues, in deaerated CH3CN and in the presence of Ag 2SO4, was performed. In particular: (i) 1-acetamidoindan (principal product), indene, 1-indanol and 1-indanone were obtained from indan; (ii) 5-methoxyindan gave 6-methoxyindene (principal product) and 5-methoxy-1-indanone; (iii) 2,3-dihydrobenzofuran, 2,3-dihydroindole and 2,3-dihydrobenzothiophene produced benzofuran, indole and benzothiophen (the last one accompanied by minor amounts of 2,3-dihydrobenzothiophene-1-oxide), respectively. Considering the previous studies on photo-oxidation of analogous substrates as benzylic derivatives (arenes, alcohols and ethers) and from reaction product profiles, an electron-transfer mechanism (from the substrate to the photogenerated hole) is suggested, where the radical cation intermediate should deprotonate to a benzylic radical. The carbocation obtained from the oxidation of this radical should competitively evolve to alkene, alcohol and acetamide. H218O labelling photo-oxidation experiments suggest that the ketone, when present, should derive from the substrate, through the alcohol as intermediate. Copyright
- Bettoni, Marta,Giacco, Tiziana Del,Rol, Cesare,Sebastiani, Giovanni V.
-
p. 359 - 364
(2007/10/03)
-
- Multicyclic bis-amide MMP inhibitors
-
The present invention relates generally to bis-amide group containing pharmaceutical agents, and in particular, to multicyclic bis-amide MMP-13 inhibitor compounds. More particularly, the present invention provides a new class of MMP-13 inhibiting compounds, containing a pyrimidinyl bis-amide group in combination with a heterocyclic moiety, that exhibit an increased potency and solubility in relation to currently known bis-amide group containing MMP-13 inhibitors.
- -
-
Page/Page column 114
(2008/06/13)
-
- Meldrum's acids as acylating agents in the catalytic intramolecular Friedel-Crafts reaction
-
(Chemical Equation Presented) The intramolecular Friedel-Crafts acylation of aromatics with Meldrum's acid derivatives catalyzed by metal trifluoromethanesulfonates is reported. Meldrum's acids are easily prepared, functionalized, handled, and purified. The synthesis of polysubstituted 1-indanones from benzyl Meldrum's acids was investigated thoroughly, and it was shown that a variety of catalysts were effective, while accommodating a diversity of functional groups under mild conditions. The scope, limitations, and functional group tolerance (terminal alkene and alkyne, ketal, dialkyl ether, dialkyl thioether, aryl methyl ether, aryl TIPS and TBDPS ethers, nitrile- and nitro-substituted aryls, alkyl and aryl halides) for a variety of 5-benzyl (enolizable Meldrum's acids) and 5-benzyl-5-substituted Meldrum's acids (quaternized Meldrum's acids), forming 1-indanones and 2-substituted-1- indanones, respectively, are delineated. This method was further applied to the synthesis of 1-tetralones, 1-benzosuberones, and the potent acetylcholinesterase inhibitor donepezil. Rate of cyclization as a function of ring size was established for various benzocyclic ketones via competition experiments: 1-tetralones form faster than both 1-indanones and 1-benzosuberones, and 1-benzosuberones cyclize faster than 1-indanones.
- Fillion, Eric,Fishlock, Dan,Wilsily, Ashraf,Goll, Julie M.
-
p. 1316 - 1327
(2007/10/03)
-
- Synthesis of 1-indanones by intramolecular Friedel-Crafts reaction of 3-arylpropionic acids catalyzed by Tb(OTf)3
-
Intramolecular Friedel-Crafts acylation reaction of 3-arylpropionic acids was efficiently catalyzed by Tb(OTf)3 at 250°C to give 1-indanones. Even deactivated 3-arylpropionic acids with halogen atoms on the aromatic ring can be cyclized in moderation to good yields.
- Cui, Dong-Mei,Zhang, Chen,Kawamura, Masato,Shimada, Shigeru
-
p. 1741 - 1745
(2007/10/03)
-
- Convenient Access to Polysubstituted 1-Indanones by Sc(OTf) 3-Catalyzed Intramolecular Friedel-Crafts Acylation of Benzyl Meldrum's Acid Derivatives
-
(Matrix presented) The intramolecular Friedel-Crafts acylation of benzyl Meldrum's acids is catalyzed by Sc(OTf)3 under mild reaction conditions. Several polysubstituted 1-indanones have been prepared.
- Fillion, Eric,Fishlock, Dan
-
p. 4653 - 4656
(2007/10/03)
-
- A study on the conversion of indanones into carbostyrils
-
We have surveyed the utility of Beckmann rearrangement for the conversion of indanones into carbostyrils. Initial attempts at the conversion of 6-methoxy indanone oxime under classical conditions resulted in the formation of the two unusual products: 2-sulfonyloxyindanone and the dimeric product. This unusual rearrangement was also observed by the treatment of some metal triflates species. Further investigation has led to the development of reliable conditions starting from oxime mesylate (not oxime tosylate), in which some strong Lewis acid catalyst (ZrCl4) was employed in either a conventional or non-conventional solvent system. The advantage of the new protocol is highlighted by the simple work up and direct isolation of the product in 65% isolated yield.
- Torisawa, Yasuhiro,Nishi, Takao,Minamikawa, Jun-Ichi
-
p. 2205 - 2209
(2007/10/03)
-
- Low temperature, high conversion, liquid-phase benzylic oxidation with dioxygen by metal/NHPI-catalyzed co-oxidation with benzaldehyde
-
A new liquid-phase catalytic oxidation system for the low temperature, high conversion benzylic mono-oxyfunctionalization of 10,11-dihydrocarbamazepine (1) into oxcarbazepine (4) with dioxygen has been developed. The method is based on a co-oxidation of 1 with benzaldehyde in the presence of a four-component catalyst system consisting of Co(OAc)2, Ni(OAc)2, Cr(NO3)3, and N-hydroxyphthalimide (NHPI). The influence of the catalyst system on the formation and decomposition of the crucial hydroperoxide intermediate 2 has been investigated. Based on these results, the role of each of the components in the catalyst system is discussed. The scope of this method for the oxidation of other substrates has been studied, and the results are compared with those obtained by Co/NHPI catalyzed oxidation of these substrates. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- De Vondervoort, Lizette Schmieder-van,Bouttemy, Sabine,Heu, Ferdinand,Weissenboeck, Kurt,Alsters, Paul L.
-
p. 578 - 586
(2007/10/03)
-
- Ketone-derivatives of indene, dihydronaphthalene or naphthalene compounds for the treatment of hyperlipidemia
-
The present application relates to a series of compounds, and pharmaceutical formulations thereof, of the formula which provide a method of inhibiting hyperlipidemia, especially hypercholesterolemia, and the pathological sequelae thereof, in mammals, including humans.
- -
-
-
- Acid-promoted fries rearrangements of benzannulated lactones
-
The scope of acid-promoted Fries rearrangements of benzannulated lactones has been examined. The reaction is applicable to seven-membered lactones possessing a sufficiently activated aromatic ring but not to six-membered lactones, and it proceeds in higher yield for diterpenoid lactones than for lower molecular weight lactones. The structures of the 2,6-methano-bridged benzoxocin side products (23), (24), and (25) from rearrangement of the diterpenoid lactone (11) have been assigned.
- Cambie, Richard C.,Mitchell, Lorna H.,Rutledge, Peter S.
-
p. 1167 - 1174
(2007/10/03)
-
- Selective oxidation of benzylic hydrocarbons to carbonyl compounds catalyzed by Mn(III) salen complexes
-
Selective oxidation of benzylic hydrocarbons to the carbonyl compounds was achieved using a racemic Mn(III) salen complex 1 as the catalyst. The reaction proceeds in good yields under mild reaction conditions using iodosobenzene or aq. sodium hypochlorite as a stoichiometric oxidant.
- Lee, Nam Ho,Lee, Chang-Seob,Jung, Duk-Sang
-
p. 1385 - 1388
(2007/10/03)
-
- Heterogeneous Permanganate Oxidations. 7. the Oxidation of Aliphatic Side Chains
-
Alkylbenzene side chains are oxidized at the benzylic position when treated under heterogeneous conditions with permanganate adsorbed on a solid support. The products are alcohols if the benzylic carbon is tertiary, or ketones if it is secondary. Carbon-carbon bond cleavage, which usually occurs when these same compounds are oxidized by permanganate under homogeneous conditions, does not occur. A unique selectivity is observed for the oxidation of derivatives of indane, 1, and tetralin, 2, in which one of the methylenes is replaced by an oxygen. If the oxygen is in the α-position, no reaction occurs; if it is in the β-position, good yields of the corresponding lactone are obtained. A mechanism consistent with the observed selectivity has been proposed.
- Noureldin, Nazih A.,Zhao, Dongyuan,Lee, Donald G.
-
p. 8767 - 8772
(2007/10/03)
-
- Heterogeneous permanganate oxidations; part 6: Selective oxidation of arenes
-
Potassium permanganate adsorbed on alumina selectively oxidizes arenes at the benzylic position. If the benzyl carbon is secondary, ketones are obtained in good yields; alcohols are produced if the benzylic position is tertiary. Benzopyranoid and benzofuranoid systems exhibit highly selective oxidation patterns. Decarboxylation occurs when phenylacetic acid is oxidized, but not when the corresponding ester, ethyl phenylacetate, is oxidized to ethyl benzoylformate.
- Zhao,Lee
-
p. 915 - 916
(2007/10/02)
-
- An unusual C-C bond cleavage with chromium VI reagents: Oxidation of primary alcohols to ketones
-
Oxidation of 1-hydroxymethylindanes and 1-hydroxymethyltetralins with PDC or PCC in methylene chloride affords 1-indanones and 1-tetralones.
- Bijoy,Subba Rao
-
p. 2701 - 2708
(2007/10/02)
-
- Rhodium Complex-Catalyzed Desilylative Cyclocarbonylation of 1-Aryl-2-(trimethylsilyl)acetylenes: A New Route to 2,3-Dihydro-1H-inden-1-ones
-
Under water gas shift reaction conditions, 1-aryl-2-(trimethylsilyl)acetylenes undergo Rh-catalyzed desilylative cyclocarbonylation to give 2,3-dihydro-1H-inden-1-ones and trimethylsilanol.A wide variety of functional groups, such as methoxy, chloro, acetyl, ethoxycarbonyl, cyano, and trifluoromethyl, are tolerated on the aromatic ring under the reaction conditions.The products were obtained in good to excellent yield whether the substituent on the aromatic ring was electron-donating or electron-withdrawing.The cyclizations of substrates bearing a meta substituent onthe aromatic ring regiospecifically gave 5-substituted-2,3-dihydro-1H-inden-1-ones except when the meta substituent was a methoxy group.The desilylative cyclocarbonylation is an alternative to the conventional preparation of 2,3-dihydro-1H-inden-1-ones, an intramolecular Friedel-Crafts acylation.A possible mechanism for the process is described.
- Takeuchi, Ryo,Yasue, Hiroyuki
-
p. 5386 - 5392
(2007/10/02)
-
- Process for preparing a 2,3-dihydro-1H-imidazolyl-ethoxy indene antithrombotic agent and its pharmaceutically acceptable salts
-
A process is disclosed for preparing a 2,3-dihydro-1H-imidazolylethoxy indene antithrombotic agent and its pharmaceutically acceptable salts.
- -
-
-
- AROMATIC ANNULATION WITH BISPHENYLTHIONIUM IONS
-
The chemospecific production and intramolecular aromatic electrophilic substitution (annulation) of bis(phenylthio)carbocations (bisphenylthionium ions) has been studied using appropriate model compounds.The annulation reaction is very sensitive to the Lewis acid initiator and also the solvent.The best reaction conditions were found to be a suspension of silver trifluoromethanesulfonate in dichloromethane.Annulation of six-membered rings onto alkylbenzene and five- and seven-membered rings onto activated benzenes have been achieved.
- Manas, Abdul Rahman Bin,Smith, Robin A. J.
-
p. 1847 - 1856
(2007/10/02)
-
- Substituent Effect in Solvolysis of Spiro-1'-yl p-Nitrobenzoate
-
The preparation of a series of substituted spiro-1'-yl p-nitrobenzoates (4a-g) is described.The solvolysis rate constant is k = 8.53 * 10-5 s-1 at 25 deg C in 80percent aqueous acetone for the unsaturated derivative (4e) and is relatively high in comparison with the related secondary systems.The Hammett treatment (ρ?+) gives a straight line and the ρ value (-3.33) is more negative than that (-2.11) of 3,4-benzotricyclo1,6>-dec-3-en-2-anti-yl p-nitrobenzoate (1).On the basis of the results, it can be considered that the mesomeric transmission of substituent effect is very weak in 1 relative to 4.
- Ohkata, Katsuo,Akiyama, Masaki,Wada, Kenshi,Sakaue, Shun,Toda, Yoshiko,Hanafusa, Terukiyo
-
p. 2517 - 2520
(2007/10/02)
-
- 3-NITROCYCLOALKENONES, SYNTHESIS AND USE AS REVERSE AFFINITY CYCLOALKYNONE EQUIVALENTS
-
A partical synthesis of 3-nitrocycloalkenones and their utilization as dienophiles in the Diels-Alder reaction are discribed.The results demonstrate a reverse affinity equivalency between these β-nitro-enones and "cycloalkynones".
- Corey, E. J.,Estreicher, Herbert
-
p. 603 - 606
(2007/10/02)
-
- Studies in Antifertility Agents: Part XXV - 2-Carboxy-7-hydroxy-1-phenyl-1,2,3,4-tetrahydrofluorene
-
The synthesis and stereochemical assignments of 2-carboxy-7-hydroxy-1-phenyl-1,2,3,4-tetrahydrofluorene (17) are reported. 2-Arylidene-5-methoxy-1-indanones (5-8) have been prepared by condensation of 5-methoxy-1-indanone (1) with araldehydes (2-4).Addition of methyl acetoacetate onto 5 furnishes 2-carbomethoxy-7-methoxy-3-oxo-1-phenyl-1,2,3,9a-tetrahydrofluorene (9), which under acid hydrolysis gives the enone (10), and on treatment with ethanedithiol affords the thioketal (11).Desulphurization of 11 with Raney nickel yields 1,2-trans-2-carbomethoxy-7-methoxy-1-phenyl-1,2,3,4-tetrahydrofluorene (12).Catalytic hydrogenation of 12 affords possibly B/C-cis-1,2-trans-1,2,3,4,4a,9a-hexahydrofluorene (13).Alkaline hydrolysis of esters 11, 12 and 13 gives the corresponding acids 15, 16 and 14.Demethylation of 16 with BBr3-CH2Cl2 furnishes the title hydroxy acid (17).None of these compounds prevents pregnancy at a dose of 10 mg/kg in rats.
- Tewari, S. C.,Rastogi, Shri Nivas,Anand, Nitya
-
p. 139 - 142
(2007/10/02)
-
- Novel antifertility agents
-
Derivatives of 2-aroyl-3-phenylindenes, 3-aroyl-4-phenyl-1,2-dihydronaphthalenes, and 1-phenyl-2-aroyl-naphthalenes are useful as antifertility agents.
- -
-
-
