cas 925-90-6, ETHYLMAGNESIUM BROMIDE | Articles data

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Synthesis and structures of titanium complexes bearing tetradentate tripodal [O2XC] ligands (X = C, P)
We report the synthesis and structures of titanium complexes supported by tripodal mixed-donor [O2CC] and [O2PC] ligands. Stepwise cyclometallation of a chelating bis(phenoxide) complex led to tetradentate binding of the [O2CC] ligand to the titanium center. Phosphination of a Ti-C bond of the [O2CC] complex afforded the tripodal [O2PC] ligand.
Nakanishi, Yusuke,Ishida, Yutaka,Kawaguchi, Hiroyuki
p. 27 - 30
(2019)
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4-Alkyl-3-azidomethyl-2-ethoxy-2,5-dihydro-5 H-1,2-oxaphosphole 2-Oxides: Synthesis and 1,3-Cycloaddition
Starting from phosphorylated allenes, a three-steps synthesis of a new class of organic azides with a 1,2-oxaphospholene carbon skeleton has been developed. The series of obtained 4-alkyl-3-azidomethyl-2-ethoxy-2,5-dihydro-5H-1,2-oxaphosphole 2-oxides were utilized in the 1,3-cycloaddition with alkyl 2-[1-(propyn-2-yl)-1H-indol-3-yl]-2-oxoacetates for the synthesis of conjugates, which are potentially active cytostatics.
Alekseychuk, Ekaterina P.,Anikina, Lada V.,Artyushin, Oleg I.,Brel, Valery K.
supporting information

(2021/11/04)

Scalable Continuous Synthesis of Grignard Reagents from in Situ-Activated Magnesium Metal
The continuous synthesis of Grignard reagents has been investigated under continuous processing conditions using Mg turnings at variable liquid throughputs and concentrations. A novel process window easily accessible through continuous processing was employed, namely, using a large molar access of Mg turnings within the reactor and achieving Mg activation by mechanical means. A laboratory and a 10-fold-increased pilot-scale reactor setup were built and evaluated, including integrated inline analytics via ATR-IR measurements. The main goal of this work was to explore the full potential of classic Grignard reagent formation through the use of scalable flow chemistry and to allow for fast and safe process optimization. It was found that on both the laboratory and pilot scales, full conversion of the employed halides could be achieved with a single passage through the reactor. Furthermore, Grignard reagent yields of 89-100% were reached on the laboratory scale.
Deitmann, Eva,G?ssl, Lars,Hofmann, Christian,L?b, Patrick,Menges-Flanagan, Gabriele
p. 315 - 321
(2020/03/10)

Disposable cartridge concept for the on-demand synthesis of turbo Grignards, Knochel–Hauser amides, and magnesium alkoxides
Magnesium organometallic reagents occupy a central position in organic synthesis. The freshness of these compounds is the key for achieving a high conversion and reproducible results. Common methods for the synthesis of Grignard reagents from metallic magnesium present safety issues and exhibit a batch-to-batch variability. Tubular reactors of solid reagents combined with solution-phase reagents enable the continuous-flow preparation of organomagnesium reagents. The use of stratified packed-bed columns of magnesium metal and lithium chloride for the synthesis of highly concentrated turbo Grignards is reported. A low-cost pod-style synthesizer prototype, which incorporates single-use prepacked perfluorinated cartridges and bags of reagents for the automated on-demand lab-scale synthesis of carbon, nitrogen, and oxygen turbo magnesium bases is presented. This concept will provide access to fresh organomagnesium reagents on a discovery scale and will do so independent from the operator’s experience in flow and/or organometallic chemistry.
Adamo, Andrea,Berton, Mateo,McQuade, D. Tyler,Sheehan, Kevin
supporting information
p. 1343 - 1356
(2020/07/10)

Ni-Catalyzed β-Alkylation of Cyclopropanol-Derived Homoenolates
Metal homoenolates are valuable synthetic intermediates which provide access to β-functionalized ketones. In this report, we disclose a Ni-catalyzed β-alkylation reaction of cyclopropanol-derived homoenolates using redox-active N-hydroxyphthalimide (NHPI) esters as the alkylating reagents. The reaction is compatible with 1°, 2°, and 3° NHPI esters. Mechanistic studies imply radical activation of the NHPI ester and 2e β-carbon elimination occurring on the cyclopropanol.
Mills, L. Reginald,Zhou, Cuihan,Fung, Emily,Rousseaux, Sophie A. L.
supporting information
p. 8805 - 8809
(2019/11/03)

Optimization of Pyrazoles as Phenol Surrogates to Yield Potent Inhibitors of Macrophage Migration Inhibitory Factor
Macrophage migration inhibitory factor (MIF) is a proinflammatory cytokine that is implicated in the regulation of inflammation, cell proliferation, and neurological disorders. MIF is also an enzyme that functions as a keto–enol tautomerase. Most potent MIF tautomerase inhibitors incorporate a phenol, which hydrogen bonds to Asn97 in the active site. Starting from a 113-μm docking hit, we report results of structure-based and computer-aided design that have provided substituted pyrazoles as phenol alternatives with potencies of 60–70 nm. Crystal structures of complexes of MIF with the pyrazoles highlight the contributions of hydrogen bonding with Lys32 and Asn97, and aryl–aryl interactions with Tyr36, Tyr95, and Phe113 to the binding.
Trivedi-Parmar, Vinay,Robertson, Michael J.,Cisneros, José A.,Krimmer, Stefan G.,Jorgensen, William L.
supporting information
p. 1092 - 1097
(2018/04/30)

Synthetic method for 3-methylpropiophenone
The invention specifically relates to a synthetic method for 3-methylpropiophenone, belonging to the technical field of organic synthesis. The synthetic method comprises the following steps: (1) preparation of a Grignard reagent; (2) treatment of the Grignard reagent; (3) preparation of 3-methylphenylpropanol; and (4) (3) preparation of 3-methylpropiophenone. With such a technical scheme, the synthetic method can effectively overcome the disadvantages of difficulty in removal of solvents and low product yield in the prior art.
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Paragraph 0022; 0028; 0034; 0040; 0046

(2017/10/07)

A Short Access to Symmetrically α,α-Disubstituted α-Amino Acids from Acyl Cyanohydrins
A straightforward synthesis of symmetrically α,α-disubstituted α-amino acids is presented. The key step of this process relies on the efficient double addition of Grignard reagents to acyl cyanohydrins to provide N-acyl amino alcohols selectively in good yields. The chemoselectivity of the reaction was modulated by the nature of the acyl moiety. Eleven amino acids were prepared, including the particularly simple divinylglycine, which is not easily accessible by using conventional methods.
Boukattaya, Fatma,Caillé, Julien,Ammar, Houcine,Rouzier, Florian,Boeda, Fabien,Pearson-Long, Morwenna S. M.,Bertus, Philippe
p. 906 - 916
(2016/03/12)

PROCESS OF PREPARING GRIGNARD REAGENT
A novel process of preparing a Grignard reagent is disclosed. The process is effected by electrochemically reacting a Grignard precursor with an electrode which comprises a metal for forming the Grignard reagent, in the presence an electrolyte solution that comprises a room temperature ionic liquid (RTIL). Electrochemical cells and systems for performing the process, and uses thereof in various applications are also disclosed.
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Paragraph 0306-0313

(2014/05/25)

Fluoro-ene reaction versus [2+2] cycloaddition in the thermal C 2-C6 cyclization of enyne-allenes: An experimental and theoretical investigation
A series of fluoroalkyl-substituted enyne-allenes have been synthesized by a new route with the aim of elucidating the possibility of a fluoro-ene reaction via an intermediate fulvenyl diradical generated in the thermal C 2-C6 (Schmittel) cyclization reaction. As a result of the strong C-F bond, fluorine atom transfer was not observed. Instead, 1H-cyclobuta[a]indenes were formed in good yields despite the high strain energy. DFT calculations at the B3LYP level of theory indicated that although the fluoro-ene reaction is the most exothermic reaction available, cyclobutene formation is kinetically favored over the [1,5]-fluorine shift by 5-15 kcal mol-1 in various model compounds. Copyright
Cinar, M. Emin,Vavilala, Chandrasekhar,Jaquet, Ralph,Bats, Jan W.,Schmittel, Michael
p. 5166 - 5177
(2014/10/15)

COMPOSITIONS AND METHODS FOR THE TREATMENT OF NEUROLOGICAL DISEASES
The invention relates to the compounds of formula (I) or its pharmaceutica! acceptable salts, as well as polymorphs, solvates, enantiomers, stereoisomers and hydrates thereof. The pharmaceutical compositions comprising an effective amount of compounds of formula (I), and methods for the treatment of neurological diseases may be formulated for oral, buccal, rectal, topical, transdermal, transmucosal, intravenous, parenteral administration, syrup, or injection. Such compositions may be used to treatment of depressive disorders, anxiety disorders, attention deficit hyperactivity disorder, migraine prophylaxis, eating disorders, bipolar disorder, post-herpetic neuralgia, insomnia, ankylosing spondylitis, recurring biliary dyskinesia, nocturnal enuresis, cyclic vomiting syndrome, post-traumatic stress disorder (PTSD) and neuropathy.
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Paragraph 0095

(2013/12/03)

Functionalized α-bromocyclopropylmagnesium bromides: Generation and some reactions
Functional derivatives of gem-dibromocyclopropanes (ethers and esters of gemdibromocyclopropylmethanol, 2,2-dibromocyclopropanecarboxylic acids and their esters) undergo partial hydrodebromination at the treatment with isopropyl magnesium bromide (3-6 mol-equiv) in THF and then in methanol at -60°C affording the corresponding monobromides in 64-95% yields. The addition of nonsolvated magnesium bromide to the reaction mixture results in the considerable reduction of the amount of the Grignard reagent (from 6 to 3 mol-equiv). This allows achieving the partial hydrodebromination of 2,2-dibromocyclopropanecarboxylic acids. Pleiades Publishing, Ltd., 2013.
Bolesov,Solov'eva,Baird
p. 1580 - 1589
(2014/02/14)

Microwave-assisted synthesis of some novel 1,2,3-triazoles by click chemistry, and their biological activity
Five mandipropamid analogues were designed and synthesized via "click chemistry". The phenyl ring of mandipropamid was substituted by a 1,2,3-triazole functional group. Bioassay results indicated that some of the title compounds had moderate fungicidal activity.
Su, Na-Na,Li, Yao,Yu, Shu-Jing,Zhang, Xiao,Liu, Xing-Hai,Zhao, Wei-Guang
p. 759 - 766
(2013/07/27)

How big is a Cp? Cycloheptatrienyl zirconium complexes with bulky cyclopentadienyl and indenyl ligands
A combination of phase-transfer and traditional alkylation strategies has been employed to synthesise sterically encumbered 1,3-di(cyclohexyl) and 1,3-di(tert-butyl) substituted indenes in multi-gram quantities. These indenyl ligands and sterically demanding alkyl cyclopentadienyl ligands have been used to prepare a series of [(η7-C7H7) Zr(η5-L)] (L = Cp and Ind) complexes by straightforward salt metathesis between [(η7-C7H7)ZrCl(tmeda)] and the corresponding sodium indenide or cyclopentadienide. All of these Zr complexes have been characterized by elemental analysis, NMR spectroscopy and single crystal X-ray diffraction. The structural information derived from these studies was employed to evaluate the steric demand of these ligands in a realistic manner.
Gloeckner, Andreas,Bauer, Heiko,Maekawa, Miyuki,Bannenberg, Thomas,Daniliuc, Constantin G.,Jones, Peter G.,Sun, Yu,Sitzmann, Helmut,Tamm, Matthias,Walter, Marc D.
experimental part
p. 6614 - 6624
(2012/07/13)

Enantioselective copper-catalysed allylic alkylation of cinnamyl chlorides by Grignard reagents using chiral phosphine-phosphite ligands
The copper(I)-catalysed SN2'-type allylic substitution of E-3-aryl-allyl chlorides (cinnamyl chlorides) using Grignard reagents represents a powerful method for the synthesis of compounds carrying a benzylic stereocentre. By screening a small library of modular chiral phosphine-phosphite ligands a new copper(I)-based catalyst system was identified which allows the performance of such reactions with exceptional high degrees of regio- and enantioselectivity. Best results were obtained using TADDOLderived ligands (3 mol%), copper(I) bromide?dimethyl sulfide (CuBr?SMe2) (2.5 mol%) and methyl tert-butyl ether (MTBE) as a solvent. Various (1- alkyl-allyl)benzene derivatives were prepared with up to 99% ee (GC) in isolated yields of up to 99%. In most cases the product contained less than 3% of the linear regioisomer (except for ortho-substituted substrates). Both electron-rich and electron-deficient cinnamyl chlorides were successfully employed. The absolute configuration of the products was assigned by comparison of experimental and calculated CD spectra. The substrates were prepared from the corresponding alcohols by reaction with thionyl chloride. Initially formed mixtures of regioisomeric allylic chlorides were homogenised by treatment with CuBr?SMe2 (2.5 mol%) in the presence of triphenyl phosphine (PPh3) (3 mol%) in MTBE at low temperature to give the pure linear isomers. In reactions with methylmagnesium bromide (MeMgBr) an ortho-diphenylphosphanyl-arylphosphite ligand with an additional phenyl substituent in ortho'-position at the aryl backbone proved to be superior. In contrast, best results were obtained in the case of higher alkyl Grignard reagents (such as ethyl-, n-butyl-, isopropyl-, and 3-butenylmagnesium bromides) with a related ligand carrying an isopropyl substituent in ortho'-position. The method was tested on a multimmol scale and is suited for application in natural product synthesis.
Loelsberg, Wibke,Ye, Shute,Schmalz, Hans-Guenther
supporting information; experimental part
p. 2023 - 2031
(2010/10/21)

First examples of hydroxycyclopropanation in the series of lupane triterpenoids
Hydroxycyclopropanation at the ester group in the series of lupane triterpenoids was performed for the first time using 3,3-ethylenedioxybetulonic acid methyl ester and its 20,29-dihydro analog as substrates.
Odinokov,Shakurova,Khalilov,Dzhemilev
body text
p. 1464 - 1467
(2010/03/24)

Novel Pyridine Derivatives
The invention relates to novel pyridine derivatives, their preparation and their use as pharmaceutically active compounds. Said compounds particularly act as immunosuppressive agents.
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Page/Page column 12-13

(2009/01/24)

Triphenylene Compounds, Method of Manufacturing the Same and Organic Electroluminescent Devices Employing the Same
The present invention provides a novel compound represented by general formula (I) below, a method of manufacturing the same and an organic electroluminescent device employing the same; where R1 to R6 are independent of one another and are each a hydrogen atom or a substituent represented by general formula (II) below, and at least one of R1 to R6 is a substituent represented by general formula (II): [in-line-formulae]—C≡C—SiRaRbRc ??(II)[/in-line-formulae] where Ra, Rb and Rc are independent of one another and are each an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group.
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(2008/12/04)

Novel imidazo based heterocycles
The present invention is directed to novel imidazopyrazine compounds useful as kinase inhibitors and as such would be useful in treating certain conditions and diseases, especially inflammatory conditions and diseases and proliferative disorders and conditions, for example, cancers.
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Page/Page column 20

(2008/12/07)

Process for the preparation of cyclopropane derivatives with special metal oxides
Preparation of cyclopropane derivative (I) comprises reaction of alkanecarbonic acid derivative (II) with a Grignard compound (IV) or lithium compound (IVa) in the presence of a metal compound (III). Preparation of cyclopropane derivative of formula (I) comprises reaction of alkanecarbonic acid derivative of formula (II) with a Grignard compound (IV) of formula (R 1>R 2>CH-CR 3>R 4>-MgZ) or lithium compound (IVa) of formula (R 1>R 2>CH-CR 3>R 4>-Li) in the presence of a metal compound (III) of formula (Hal nM(OR 7>) 5-n). Either R, R 1>-R 4>H, 1-18C alkyl (including cycloalkyl) or 6-10C aryl; or R 1>R 2>, R 3>R 4>4-18C cyclo alkane ring; X : OH or Y 1>R 5>R 6>; Y 1>O or N; R 5>, R 6>1-18C alkyl or 6-10C aryl; M : V, Nb or Ta (preferred); Hal, Z : Cl (preferred), Br or I; R 7>1-8C alkyl residue; and n : 0-5 (preferably 0). Provided that when Y 1> is O then R 6> is absent and X is OH. [Image] [Image] ACTIVITY : Plant Protectant. MECHANISM OF ACTION : None given.
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Page/Page column 4

(2010/11/08)

Alkoxysilacycloalkanes, process for their preparation and their use for the polymerization of olefins
The invention relates to alkoxysilacycloalkanes, to the process of their preparation and to their use in the polymerization of olefins. The introduction of these alkoxysilacycloalkanes into the olefin polymerization environment makes it possible to raise the heptane-insolubles content of the polymer finally formed.
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Page/Page column 14

(2010/11/30)

Grignard exchange reaction using a microflow system: From bench to pilot plant
The Grignard exchange reaction of ethylmagnesium bromide (EtMgBr) and bromopentafluorobenzene (BPFB) to give pentafluorophenylmagnesium bromide (PFPMgBr) was carried out using small- and medium-scale microflow systems consisting of a micromixer and a microheat exchanger. The results indicate that the microflow systems are quite effective. On the basis of the data obtained, a pilot that involves the Toray Hi-mixer connected to a shell and tube microheat exchanger was constructed. Continuous operation for 24 h was accomplished without any problem to obtain pentafluorobenzene (PFB) after protonation (92% yield).
Wakami, Hideo,Yoshida, Jun-Ichi
p. 787 - 791
(2012/12/26)

AN IMPROVED PROCESS FOR THE PREPARATION OF TERBINAFINE INTERMEDIATE
This application discloses an improved process for the preparation of N-methyl-N-(1-naphthylmethyl)-6,6-dimethyl-2-hydroxyheptan-4-ynyl-1-amine, a key intermediate used in the synthesis of terbinafine ((E)-N-(6,6-dimethyl-2-hepten-4-ynyl)-N-methyl-1-naphthalenemethanamine). Process is involving converting tertiary-butylacetylene to its Grignard derivative via transmetallation using lower alkylmagnesium halides and treating it with 1-[N-methyl-N-(1-naphtylmethyl)amino]-2,3-epoxypropane at -10°C to -20°C, slowly heating the reaction mass to reflux temperature and quenching of reaction mass with ammonium chloride to give the compound of the formula-I as crystalline solid.
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Page/Page column 7

(2010/02/12)

Process for the synthesis of 1-(3,5-bis(trifluoromethyl)-phenyl)ethan-1-one
The present invention is concerned with a novel process for the preparation of 1-(3,5-bis(trifluoromethyl)phenyl)ethan-1-one (CAS 30071-93-3). This compound is useful as an intermediate in the synthesis of therapeutic agents.
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(2008/06/13)

Pyrido-pyrido-pyrrolo pyrrolo-indole and pyrido-pyrrolo pyrrolo carbazole derivatives, method for the production thereof and pharmaceutical compositions containing said derivatives
Compounds of formula (I): wherein: W1 and W2, together with the carbon atoms to which they are bonded, represent a phenyl group or a pyridyl group, and at least one of the groups W1 or W2 represents a pyridyl group, R1 and R2 each represent a group of formula U-V as defined in the description, X and X1 each represent a hydrogen atom or a hydroxy, alkoxy, mercapto or alkylthio group, Y and Y1 each represent a hydrogen atom, or X and Y, X1 and Y1, together with the carbon atom carrying them, represent a carbonyl or thiocarbonyl group, R4 and R5 are as defined in the description, Q1, Q2 represent a hydrogen atom, or Q1 and Q2, together with the carbon atoms carrying them, form an aromatic bond. Medicaments.
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Page 10

(2010/02/08)

Phthalazine derivatives as phosphodiesterase 4 inhibitors
Compounds of formula (I) wherein B is alkylene, amino, CONH or a bond; Cy is optionally substituted phenyl or heteroaryl; R is H, phenyl or (C1-4)alkyl optionally substituted; R1is (C1-6)alkyl or polyfluoro(C1-6)-alkyl; R2is (C4-7)cycloalkyl optionally containing an oxygen atom and optionally substituted; and the N→O derivatives and pharmaceutically acceptable salt thereof are PDE 4 and TNFα inhibitors.
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(2008/06/13)

Method for producing alkyl-bridged ligand systems and transition metal compounds
The invention relates to a method for producing highly substituted alkyl-bridged ligand systems on the basis of indene derivatives and transition metal compounds. Said alkyl-bridged ligand systems can be obtained in high yields using this method.
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(2008/06/13)

Production process of cyclohexenyl ketones
An economical process for producing (2- and/or 1-)cyclohexenyl methyl ketones which are intermediates for the synthesis of α- or β-damascone. In the presence of a catalyst, a 3-cyclohexenyl methyl ketone represented by the following formula (1a): wherein, R1, R2 and R3 each independently represents a hydrogen atom or a methyl group and at least two of R1, R2 and R3 are methyl groups, is isomerized.
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(2008/06/13)

Absolute kinetic rate constants and activation energies for the formation of Grignard reagents
This paper reports the first absolute rate constants for the formation of Grignard reagents from magnesium metal and organohalides. The theory that allows calculation of heterogeneous rate constants from the rate of growth of individual pits is described. By monitoring the reaction of individual reactive sites on the magnesium surface using photomicrography, it is possible to determine the rate of reaction and the active surface area; rate constants then are calculated from those data. Rate constants are on the order of 10-4 cm/s and vary relatively little between various organohalides. By measuring rate constants over a range of temperatures, Arrhenius parameters are determined for the reaction. The magnitudes of the enthalpic and entropic barriers are not consistent with electron transfer as the rate-limiting step. Rather, the data suggest that the rate-limiting step is reaction of the organohalide at the magnesium surface with partial insertion of a magnesium atom into the carbon-halide bond in the transition state.
Beals, Bridget J.,Bello, Zainab I.,Cuddihy, Kathleen P.,Healy, Ethan M.,Koon-Church, Stephanie E.,Owens, Jane M.,Teerlinck, Cynthia E.,Bowyer, Walter J.
p. 498 - 503
(2007/10/03)

Adamantanemethanol derivatives and production processes thereof
An adamantanemethanol derivative of the invention is represented by the following formula (1), wherein Rais a hydrogen atom or a hydrocarbon group; Rbis a hydrocarbon group having a carbon atom, to which carbon atom at least one hydrogen atom is bonded, at a bonding site with the adjacent carbon atom; Rc, Rdand Reare each a hydrogen atom, a hydroxyl group which may be protected by a protective group or the like; provided that a hydroxyl group protected by a protective group or the like is bonded to at least one carbon atom constituting the adamantane skeleton when Rais a hydrogen atom or a methyl group and Rbis a methyl group; and at least one substituent, in addition to the HO—C(Ra)(Rb)— group indicated in the formula (1), is bonded to the adamantane ring when one of Raand Rbis a methyl group and the other is an ethyl group.
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Example 3

(2008/06/13)

2,3-oxidosqualene-lanosterol cyclase inhibitors
The present invention relates to aminocyclohexanol derivatives useful for the treatment and/or prophylaxis of diseases which are associated with 2,3-oxidosqualene-lanosterol cyclase such as hypercholesterolemia, hyperlipemia, arteriosclerosis, vascular diseases, mycoses, gallstones, tumors and/or hyperproliferative disorders, and treatment and/or prophylaxis of impaired glucose tolerance and diabetes.
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(2008/06/13)

Oxazolidinone antibacterial agents having a thiocarbonyl functionality
The present invention provides compounds of Formula 1: or pharmaceutical acceptable salts thereof wherein A, G and R1are as defined in the claims which are antibacterial agents.
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Page column 78

(2010/01/30)

An ESR and HPLC-EC assay for the detection of alkyl radicals
The correlation of lipid peroxidation with release of alkanes (RH) is considered a noninvasive method for the in vivo evaluation of oxidative stress. The formation of RH is believed to reflect a lipid hydroperoxide (LOOH)-dependent generation of alkoxyl radicals (LO·) that undergo β-scission with release of alkyl radicals (R·). Alternatively, R· could be spin-trapped with a nitrone before the formation of RH and analyzed by ESR. Extracts from the liver and lung of CCl4- and asbestos-treated rats that were previously loaded with nitrones exhibited ESR spectra suggesting the formation of iso-propyl, n-butyl, ethyl, and pentyl radical-derived nitroxides. In biological systems, various nitroxides with indistinguishable ESR spectra could be formed. Hence, experiments with N-tert-butyl-α-phenylnitrone (PBN) for spin trapping of R· were carried out in which the nitroxides formed were separated and analyzed by HPLC with electrochemical detection (EC). The C1-5 homologous series of PBN nitroxides and hydroxylamines were synthesized, characterized by ESR, GC-MS, and HPLC-EC, and used as HPLC standards. For in vivo generation and spin trapping of R·, rats were loaded with CCl4 and PBN. The HPLC-EC chromatograms of liver extracts from CCl4-treated rats demonstrated the formation of both the nitroxide and hydroxylamine forms of PBN/·CCl3, as well as the formation of a series of unidentified PBN nitroxides and hydroxylamines. However, formation of PBN adducts with retention times similar to these of the PBN/C2-5 derivatives was not observed. In conclusion, we could not correlate the production of PBN-detectable alkyl radicals with the reported CCl4-dependent production of C1-5 alkanes. We speculate that the major reason for this is the low steady-state concentrations of R· produced because only a small fraction of LO· undergo β-scission to release R·.
Novakov,Feierman,Cederbaum,Stoyanovsky
p. 1239 - 1246
(2007/10/03)

New syntheses of the rice moth and stink bug pheromones by employing (2R, 6S)-7-acetoxy-2,6-dimethyl-1-heptanol as a building block
(2R, 6R, 10R)-6,10,14-Trimethyl-2-pentadecanol, the female pheromone of the rice moth (Corcyra cephalonica), and methyl (2R, 6R, 10R)-2,6,10-trimethyltridecanoate, the male pheromone of the stink bug (Euschistus heros) were synthesized by employing (2R, 6S)-7-acetoxy-2,6-dimethyl-1-heptanol as the common chiral building block.
Nakamura, Yoshihide,Mori, Kenji
p. 1713 - 1721
(2007/10/03)

Bisaryl COX-2 inhibiting compounds, compositions and methods of use
The present invention relates to inhibitors of COX-2, compositions which contain such compounds and methods of use. The compounds are represented by formula I: STR1 and include pharmaceutically acceptable salts and esters thereof.
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(2008/06/13)

Nature of Organic Radical in Hydrocarbon Halide and Character of Its Adsorption on Magnesium Surface during Oxidation of the Metal
Adsorption of various hydrocarbon bromides on magnesium surface from a mixture of diethyl ether and benzene during magnesium oxidation was studied. The character of adsorption, the reaction rate, and the yields of the Grignard reagents are determined by the structure of the organic radical in the oxidant molecule.
Maslennikov,Spirina
p. 1876 - 1877
(2007/10/03)

Process for the preparation of polyunsaturated olefins
A process for the preparation of a polyunsaturated olefinic compound, i.e. undeca-1,3,5-triene, in its (3E,5Z) isomeric form, consisting of four consecutive steps starting from deca-1,4-diyne, is disclosed. Said process has the advantage of making it possible to obtain the desired isomer in its essentially pure form.
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(2008/06/13)

Optically active triazole derivatives and compositions
The compound (+)-2-(2,4-difluorophenyl)-1-[3-[(E)-4-(2,2,3,3-tetrafluoropropoxy)styryl]-1H-1,2,4-triazol-1-yl]-3-(1H-1,2,4-triazol-1-yl)propan-2-ol, which has antifungal activity, and is valuable in treatment of fungal infections in man and in other animals, pharmacologically acceptable salts thereof, solvates thereof and solvates of salts thereof, and also methods for its preparation, and medicinal compositions characterised in that they contain it as active ingredient. The invention also concerns intermediates for the preparation of the compound shown by the formula ((+)-I) and also methods for their preparation.
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(2008/06/13)

Hydroquinoline compounds, compositions containing same and processes for preparing same
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(2008/06/13)

Use of Magnesium Anthracene * 3 THF in Synthesis: Generation of Grignard Compounds and Other Reactions with Organic Halides
The course (a), (b), (c) (Scheme 1) of the reaction of magnesium anthracene * 3 THF (1) with organic halides (RX) is dependent on the nature of RX.With alkyl halides in THF 1 reacts as a nucleophile, whereby primary as well as secondary alkyl halides produce dialkyldihydroanthracenes (4-4'') and tertiary alkyl halides yield primarily monoalkyl-substituted dihydroanthracenes (2, 2').With bromo- and iodobenzene in THF 1 reacts predominantly as a radical with H atom abstraction from the solvent affording benzene and 9.The formation of Grignard compounds (5) and anthracene (6), originating from primary and secondary alkyl and aryl halides and 1 in toluene or ether at elevated temperatures, is not caused by the reaction of 1 but by the "active magnesium" (Mg*) formed by decomposition of 1 in these solvents.In contrast, allyl, propargyl, and benzyl halides react with 1 independently of the solvent under mild conditions to produce 5 and 6.Allyl- and the difficultly accessible allenylmagnesium chloride can be prepared in THF at -78 and 0 deg C, respectively, from the corresponding halides and ordinary Mg powder via catalytic amounts of 1.
Bogdanovic, Borislav,Janke, Nikolaus,Kinzelmann, Hans-Georg
p. 1507 - 1515
(2007/10/02)

Arylcyclobutylmethylamines
Compounds of formula I STR1 and pharmaceutically acceptable salts thereof; in which R1 and R2, which are the same or different, are H or an optionally substituted hydrocarbon group or R1 and R2 together with the nitrogen atom to which they are attached form an optionally substituted heterocyclic ring; R3 is an optionally substituted aromatic hydrocarbon group; and R4 is a hydrocarbon group containing at least one substituent selected from the group consisting of hydroxy and acylated derivatives thereof, optionally substituted alkoxy groups, optionally substituted cycloalkyloxy groups, optionally substituted alkylenedioxy groups, oxo and groups of formula S(O)p R5 in which p is 0, 1 or 2 and R5 is an alkyl group, said hydrocarbon group being optionally substituted by additional substituents, are useful in the treatment of depression.
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(2008/06/13)

Preparation of polyfluoroenolates
Polyfluoroenolates, R1 CX=CR2 OM (R1 is F or a perfluoroalkyl group, R2 is a perfluoroalkyl group, X is F, Cl or Br), are easily formed at good yields by dehydrohalogenation reaction of polyfluoroalcoholates, R1 CXY--CR2 HOM (Y is F, Cl or Br), with a strong base such as, e.g., an alkyl metal or an aryl metal. A typical example of the polyfluoroenolates is lithium pentafluoro-2-propenolate which is obtained from hexafluoro-2-propanolate. A polyfluoroenolate of the above general formula can be converted into another polyfluoroenolate having an alkyl or aryl group in place of the halogen X by reaction with an alkyl or aryl metal.
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(2008/06/13)

17-Substituted estradienes and estratrienes
17-Substituted estradienes and estratrienes of Formula I STR1 wherein STR2 R is alkyl, alkenyl or cycloalkyl of up to 5 carbon atoms if STR3 R is hydrogen, alkyl, alkenyl or cycloalkyl of up to 5 carbon atoms if STR4 is a CC-single or CC-double bond, exhibit, an aldosterone-antagonistic activity and a strong gestagen potency.
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(2008/06/13)

Benzimidazolyl-sulfinyl-tetrahydroquinolines
A hydroquinoline compound of the formula (1): STR1 wherein R1, R2, R3, A, l, m and n are as defined or its pharmaceutically acceptable salt, composition containing the compound and processes for preparing same are disclosed. The compound is useful as an antiulcer agent.
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(2008/06/13)

OXIDATION OF MAGNESIUM WITH ETHYL BROMIDE IN DIPOLAR APROTIC SOLVENTS
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Kondin, A. V.,Alyasov, V. N.,Zaburdyaev, V. S.,Maslennikov, V. P.,Baryshnikov, Yu. N.
p. 1087 - 1092
(2007/10/02)

2,3-dihydro-2,3,5-trimethyl-4H-pyran-4-one derivative and sex attractant for drugstore beetles
A 2,3-dihydro-2,3,5-trimethyl-4H-pyran-4-one derivative represented by general formula: STR1 where R is STR2 --CH(OCH3)2, --CH(OC2 H5)2, --CHO, --CH2 OH, --CH=CH2, =CHCH2 CH3, --CH=CHCH3 or STR3 The derivative is useful as a sex attractant for drugstore beetles.
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(2008/06/13)

Process for using finely divided highly reactive magnesium
The present invention relates to a process for preparing a finely divided, highly reactive magnesium from magnesium hydride, magnesium anthracene and/or its derivatives or magnesium butadiene and/or its alkyl or phenyl derivatives, which process is characterized in that the respective magnesium-containing compound is thermally decomposed at a pressure from 10-6 to 1 bar, the decomposition being carried out in the presence of a co-reactant of a consecutive reaction, or such co-reactant being added only after completion of the precipitation of the magnesium, or in the absence of such co-reactant, the magnesium obtained by said decomposition being isolated as a powder, and to the use of the finely divided, highly reactive magnesium for inserting magnesium into poorly reactive C--X bonds, wherein X denotes heteroatoms such as halogen, oxygen, sulfur, nitrogen, phosphorus, and the resulting organomagnesium compound may be used in a consecutive reaction according to a per se known method, and for the reversible preparation of active magnesium hydride by reaction with molecular hydrogen at a pressure of from 1 to 2 bar and at a temperature of from 150° C. to 250° C.
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(2008/06/13)

Metal extraction using a novel group of compounds and chemical purification method
Compounds of the formula STR1 in which; X represents a straight chain hydrocarbyl group containing from 8 to 17 carbon atoms; Y represents H or the group--CH=NOH, and Z represents H or the group--CH=NOH or the group--CPh=NOH, provided that at least one of Y and Z represents H; or such compound containing at least one electronegative substituent in the aromatic ring, may be prepared from anacardic acid and its analogues, and are useful for the extraction of copper from acidic aqueous solution. Cardanol, which has the formula STR2 where n=0, 2, 4 or 6 is recovered from cashew nut shell liquid containing cardol and other dihydric phenols by reacting the dihydric phenols in the CNSL with an aldehyde while leaving the cardanol substantially unreacted, and vacuum distilling the cardanol from the reaction mixture.
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(2008/06/13)

An unusual solvent effect in the reaction of ethylmagnesium bromide with triethylborane in ethyl ether or tetrahydrofuran. A simple direct route to tetraorganylborate complexes
The reaction of organic halides, magnesium turnings, and boron trifluoride etherate yields triorganylboranes quantitatively in anhydrous ethyl ether (modified organometallic method) but leads to quantitative formation of tetraorganylborate complexes in tetrahydrofuran. A detailed study of the reaction of ethylmagnesium bromide with triethylborane revealed that essentially no reaction occurs in ethyl ether, EtMgBr + BEt3, but complete combination occurs in tetrahydrofuran, Et4BMgBr. This development provides a simple, convenient route for the synthesis of tetraorganylborate complexes.
Brown, Herbert C.,Racheria, Uday S.
p. 391 - 393
(2008/10/08)

Liquid crystal compounds and method of preparation
Asymmetric trans-4,4'-dialkyl-ONN-azoxybenzenes having the general formula: STR1 wherein R1 and R2 are straight-chain alkyl groups having from 1 to 10 carbon atoms and R1 ≠R2 are provided. The azoxybenzene compounds are prepared by condensing corresponding P-alkylaniline STR2 and P-alkylnitrobenzene STR3 placing the reaction mixture into ammonium chloride and hydrolyzing to yield the asymmetrical azoxybenzene compound, corresponding asymmetrical azobenzene compound and asymmetric azobenzene compound. The asymmetric azoxy compound is then separated from the mixture by column chromotography and recrystallization. The asymmetric azoxybenzene compounds have a wide range of nematic liquid crystal temperature and are particularly well suited for liquid crystal compositions for use in matrix-addressing driving systems.
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(2008/06/13)