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Poor Yields (poor + yield)
Selected AbstractsRegiospecific Synthesis of 4-Deoxy- D - threo -hex-3-enopyranosides by Simultaneous Activation,Elimination of the Talopyranoside Axial 4-OH with the NaH/Im2SO2 System: Manifestation of the Stereoelectronic EffectEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 23 2006Emanuele Attolino Abstract A new and high-yielding method for the regioselective preparation of 4-deoxy- and 2,4-dideoxy-2-acetamido-,- D - threo -hex-3-enopyranosides has been developed. The process involves a simultaneous activation,elimination of the OH-4 group of ,- D -talopyranosides and 2-acetamido-2-deoxy-,- D -talopyranosides, mediated by the NaH/N,N,-sulfuryldiimidazole system at ,30 °C. The same reaction applied on the analogous ,- D -galactopyranosides takes place without any regioselectivity, affording mixtures of hex-3- and hex-4-enopyranosides. In the case of the methyl 2,3,6-tri- O -benzyl-,- D -talo- and ,- D -galactopyranosides, the corresponding 4- O -imidazylates can be isolated by quenching the reactions at ,30 °C. Upon warming these crude products to room temperature, the ,- talo -4- O -imidazylate gives the corresponding hex-3-eno derivative in very high yield, but its ,- galacto analogue gives the hex-4-enopyranoside enol ether in poor yield. The different regiochemical outcome between the talo and the galacto series has been attributed to the stereoelectronic effect exerted, exclusively in talo -configured compounds, by the axially disposed C-2 electronegative substituent, which selectively accelerates the breaking of the antiperiplanar C(3),H bond. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] The reaction OF N -dichlorophosphoryl- P -trichlorophosphazene with alkyl grignard reagentsHETEROATOM CHEMISTRY, Issue 5 2003F. Aslan The reactions of N-dichlorophosphoryl-P-trichlorophosphazene Cl3PNP(O)Cl2 (1) with benzylmagnesium bromide, 2-phenylethylmagnesium bromide, trimethylsilylmethylmagnesium chloride, n-butylmagnesium bromide, cyclohexylmagnesium bromide, cyclopentylmagnesium bromide, tert-butylmagnesium bromide, iso-propylmagnesium bromide, and ethylmagnesium bromide were studied. Tri- and pentaalkyl phosphazenes were obtained in very poor yield from trimethylsilylmethylmagnesium chloride and cyclohexylmagnesium bromide, respectively. Trialkylphosphoryl compounds formed from benzyl-, 2-phenylethyl-, and n-butylmagnesium bromide. No phosphorus compound could be isolated from the reaction of 1 with t-butyl-, cyclopentyl-, iso-propyl-, and ethylmagnesium bromide. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:413,416, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10153 [source] The effect of temperature on the stability of compounds used as UV-MALDI-MS matrix: 2,5-dihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, ,-cyano-4-hydroxycinnamic acid, 3,5-dimethoxy-4-hydroxycinnamic acid, nor-harmane and harmaneJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 2 2009Olga I. Tarzi Abstract The thermal stability of several commonly used crystalline matrix-assisted ultraviolet laser desorption/ionization mass spectrometry (UV-MALDI-MS) matrices, 2,5-dihydroxybenzoic acid (gentisic acid; GA), 2,4,6-trihydroxyacetophenone (THA), ,-cyano-4-hydroxycinnamic acid (CHC), 3,5-dimethoxy-4-hydroxycinnamic acid (sinapinic acid; SA), 9H-pirido[3,4-b]indole (nor-harmane; nor-Ho), 1-methyl-9H-pirido[3,4-b]indole (harmane; Ho), perchlorate of nor-harmanonium ([nor-Ho + H]+) and perchlorate of harmanonium ([Ho + H]+) was studied by heating them at their melting point and characterizing the remaining material by using different MS techniques [electron ionization mass spectrometry (EI-MS), ultraviolet laserdesorption/ionization-time-of-flight-mass spectrometry (UV-LDI-TOF-MS) and electrospray ionization-time-of-flight-mass spectrometry (ESI-TOF-MS)] as well as by thin layer chromatography analysis (TLC), electronic spectroscopy (UV-absorption, fluorescence emission and excitation spectrosco y) and 1H nuclear magnetic resonance spectroscopy (1H-NMR). In general, all compounds, except for CHC and SA, remained unchanged after fusion. CHC showed loss of CO2, yielding the trans-/cis -4-hydroxyphenylacrilonitrile mixture. This mixture was unambiguously characterized by MS and 1H-NMR spectroscopy, and its sublimation capability was demonstrated. These results explain the well-known cluster formation, fading (vanishing) and further recovering of CHC when used as a matrix in UV-MALDI-MS. Commercial SA (SA 98%; trans -SA/cis -SA 5 : 1) showed mainly cis- to- trans thermal isomerization and, with very poor yield, loss of CO2, yielding (3,,5,-dimethoxy-4,-hydroxyphenyl)-1-ethene as the decarboxilated product. These thermal conversions would not drastically affect its behavior as a UV-MALDI matrix as happens in the case of CHC. Complementary studies of the photochemical stability of these matrices in solid state were also conducted. Copyright © 2008 John Wiley & Sons, Ltd. [source] Molecularly Imprinted Polymer-Assisted Refolding of LysozymeBIOTECHNOLOGY PROGRESS, Issue 5 2007Mitsuru Haruki For production of active proteins using heterologous expression systems, refolding of proteins from inclusion bodies often creates a bottleneck due to its poor yield. In this study, we show that molecularly imprinted polymer (MIP) toward native lysozyme promotes the folding of chemically denatured lysozyme. The MIP, which was prepared with 1 M acrylamide, 1 M methacrylic acid, 1 M 2-(dimethylamino)ethyl methacrylate, and 5 mg/mL lysozyme, successfully promoted the refolding of lysozyme, whereas the non-imprinted polymer did not. The refolding yield of 90% was achieved when 15 mg of the MIP was added to 0.3 mg of the unfolded lysozyme. The parallel relationship between the refolding yield and the binding capacity of the MIP suggests that MIP promotes refolding through shifting the folding equilibrium toward the native form by binding the refolded protein. [source] ChemInform Abstract: The Acid-Mediated Intramolecular 1,3-Dipolar Cycloaddition of Derived 2-Nitro-1,1-ethenediamines for the Synthesis of Novel Fused Bicyclic Isoxazoles.CHEMINFORM, Issue 42 2010Lee W. Page Abstract The five-membered ring-fused compound (IIc) gives only poor yield after chromatographic work-up. [source] Further Studies on the Synthesis of meso -Tetraarylazuliporphyrins under Lindsey,Rothemund Reaction Conditions and Their Conversion into BenzocarbaporphyrinsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 23 2003Timothy D. Lash Abstract Azulene has been shown to react with pyrrole and a series of aromatic aldehydes in the presence of boron trifluoride etherate to give meso -tetraarylazuliporphyrins 6. Good yields of azuliporphyrins were obtained for benzaldehyde, 4-chlorobenzaldehyde, 4-bromobenzaldehyde, and 4-iodobenzaldehyde, and under dilute conditions p -tolualdehyde gave respectable yields. In each case, substantial amounts of meso -tetraarylporphyrins were also formed and a minor fraction of carbaporphyrin by-products could be detected, but otherwise no other macrocyclic products could be identified. 4-Nitrobenzaldehyde gave relatively poor yields of the corresponding azuliporphyrin, while p -anisaldehyde only gave trace amounts of product. Pentafluorobenzaldehyde gave variable results, although in this case a large number of additional by-products were identified including N -fused pentaphyrin, hexaphyrin, and higher order porphyrinoids, but no expanded azulene-containing macrocycles could be detected. Azuliporphyrins undergo reversible nucleophilic substitution on the seven-membered ring with pyrrolidine, benzenethiol, hydrazine, or benzylamine to give carbaporphyrin adducts. This property appears to facilitate an oxidative ring contraction of azuliporphyrins 6 with tert -butyl hydroperoxide in the presence of potassium hydroxide to produce mixtures of benzocarbaporphyrins 19 and 20. Tetraaryl-benzocarbaporphyrins exhibit slightly reduced diatropic ring currents compared to their meso -unsubstituted counterparts, although their UV/Vis spectra are very porphyrin-like and exhibit strong Soret bands near 450 nm. The benzocarbaporphyrins undergo reversible protonation to give monocationic and dicationic species. The latter involves C -protonation to generate an internal CH2 within the macrocyclic cavity. X-ray crystallography of tetraphenylbenzocarbaporphyrin 19a confirms that the preferred tautomer has the two NHs on either side of the indene subunit, in agreement with previous theoretical and spectroscopic studies. In addition, the presence of phenyl substituents at the 5,20-positions was found to tilt the indene moiety substantially by 27.4(1)° relative to the [18]annulene substructure. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Extra terminal residues have a profound effect on the folding and solubility of a Plasmodium falciparum sexual stage-specific protein over-expressed in Escherichia coliFEBS JOURNAL, Issue 21 2002Sushil Prasad Sati The presence of extra N- and C- terminal residues can play a major role in the stability, solubility and yield of recombinant proteins. Pfg27 is a 27K soluble protein that is essential for sexual development in Plasmodium falciparum. It was over-expressed using the pMAL-p2 vector as a fusion protein with the maltose binding protein. Six different constructs were made and each of the fusion proteins were expressed and purified. Our results show that the fusion proteins were labile and only partially soluble in five of the constructs resulting in very poor yields. Intriguingly, in the sixth construct, the yield of soluble fusion protein with an extended carboxyl terminus of 17 residues was several fold higher. Various constructs with either N-terminal or smaller C-terminal extensions failed to produce any soluble fusion protein. Furthermore, all five constructs produced Pfg27 that precipitated after protease cleavage from its fusion partner. The sixth construct, which produced soluble protein in high yields, also gave highly stable and soluble Pfg27 after cleavage of the fusion. These results indicate that extra amino acid residues at the termini of over-expressed proteins can have a significant effect on the folding of proteins expressed in E. coli. Our data suggest the potential for development of a novel methodology, which will entail construction of fusion proteins with maltose binding protein as a chaperone on the N-terminus and a C-terminal ,solubilization tag'. This system may allow large-scale production of those proteins that have a tendency to misfold during expression. [source] The Nonchiral Bislactim Diethoxy Ether as a Highly Stereo-Inducing Synthon for Sterically Hindered, , -Branched , -Amino Acids: A Practical, Large-Scale Route to an Intermediate of the Novel Renin Inhibitor AliskirenHELVETICA CHIMICA ACTA, Issue 8 2003Richard Göschke The diastereoselective synthesis of the sterically hindered, , -branched , -amino acid derivative (2S,4S)- 24a and its N -[(tert -butoxy)carbonyl](Boc)-protected alcohol (2S,4S)- 19, both key intermediates of a novel class of nonpeptide renin inhibitors such as aliskiren (1), is described. Initially, the analogous methyl ester (2S,4S)- 17 was obtained by alkylation of the chiral Schöllkopf dihydropyrazine (R)- 12a with the dialkoxy-substituted alkyl bromide (R)- 11a, which proceeded with explicitly high diastereofacial selectivity (ds ,98%) to give (2S,5R,2,S)- 13a (Scheme,4), followed by mild acid hydrolysis and N -Boc protection (Scheme,5). Conversely, the complete lack of stereocontrol and poor yields for the reaction of (R)- 11a with the enantiomeric (S)- 12b suggested, in addition to the anticipated shielding effect by the iPr group at C(2) of the auxiliary, steric repulsion between the MeOC(6) and the bulky residues of (R)- 11a in the proposed transition state, which would strongly disfavor both the Si and Re attack of the electrophile (see Fig.). Based on this rationale, alkylation of the readily accessible achiral diethoxy-dihydropyrazine 21 with (R)- 11a was found to provide a 95,:,5 mixture of diastereoisomers (2S,2,S)- 22a and (2R,2,S)- 23a in high yield (Scheme,6), which afforded in two steps and after recrystallization enantiomerically pure (2S,4S)- 24a. Similarly, the stereochemical course for the alkylation reactions of the related alkyl bromides (S)- 28a and (R)- 28b with both (R)- 12a and (S)- 12b as well as with the achiral 21 was investigated (Schemes,7,9). The precursor bromides (R)- 11a, (S)- 11b, (R)- 28a, and (S)- 28b were efficiently synthesized via the diastereoselective alkylation of the Evans 3-isovaleroyloxazolidin-2-ones (R)- 7a and (S)- 7b either with bromide 6 or with benzyl chloromethyl ether, and subsequent standard transformations (Schemes,3 and 7). A practical and economical protocol of the preparation of (2S,4S)- 24a on a multi-100-g scale is given. This is the first report of the application of an achiral dihydropyrazine, i.e., in form of 21, as a highly stereo-inducing synthon providing rapid access to a N -protected , -branched , -amino acid with (2S) absolute configuration. [source] Oxazoline chemistry part III.JOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 3 2003-anilinyl)-2-oxazolines], Synthesis, characterisation of [2-(, some related compounds The syntheses and characterisation of a series of chiral and achiral 2-(aminophenyl)-2-oxazolines and some related compounds is reported. All of the derivatives have been produced by a one-step procedure involving the treatment of isatoic anhydride (i.e. [2H]-3, 1-benzoxazine-[1H -2,4-dione: 1) or its 5-chloro analogue with a slight excess of appropriate amino-alcohols. In most cases, anhydrous ZnCl2 is shown to be an effective Lewis acid catalyst for this reaction at reflux temperature in high boiling aromatic solvents (PhCl or PhMe). Oxazolines have been readily formed using rac -2-amino-1-butanol, (S)-phenylglycinol, 2-methyl-2-amino-1-propanol and (1S,2R) or (IR,2S)-cis - 1 -amino-2-indanol; yields range from 85% to 22%. The use of aminoalcohols such as 2-ethanolamine, (±)-2-amino-1-phenyl-1-propanol or 3-amino-1-propanol (to give the corresponding 4,5-dihydro-1,3-oxazine) results in poor yields. The use of other Lewis acid catalysts (silicic acid, Cd(acac)2·2H2O, CuCl2·2H2O, InCl3) or higher temperatures did not improve the yields with these latter two substrates. Benzoxazoles and N-substituted benzoxazoles can also be obtained in reasonable yields from 1 using 2-aminophenol (36%) or 2-amino-3-hydroxypyridine (45%). [source] Toward a better analysis of secreted proteins: the example of the myeloid cells secretomePROTEINS: STRUCTURE, FUNCTION AND BIOINFORMATICS, Issue 11 2007Mireille Chevallet Abstract The analysis of secreted proteins represents a challenge for current proteomics techniques. Proteins are usually secreted at low concentrations in the culture media, which makes their recovery difficult. In addition, culture media are rich in salts and other compounds interfering with most proteomics techniques, which makes selective precipitation of proteins almost mandatory for a correct subsequent proteomics analysis. Last but not least, the non-secreted proteins liberated in the culture medium upon lysis of a few dead cells heavily contaminate the so-called secreted proteins preparations. Several techniques have been used in the past for concentration of proteins secreted in culture media. These techniques present several drawbacks, such as coprecipitation of salts or poor yields at low protein concentrations. Improved techniques based on carrier-assisted TCA precipitation are described and discussed in this report. These techniques have been used to analyze the secretome of myeloid cells (macrophages, dendritic cells) and enabled to analyze proteins secreted at concentrations close to 1,ng/mL, thereby allowing the detection of some of the cytokines (TNF, IL-12) secreted by the myeloid cells upon activation by bacterial products. [source] ChemInform Abstract: Negishi Alkyl,Aryl Cross-Coupling Catalyzed by Rh: Efficiency of Novel Tripodal 3-Diphenylphosphino-2-(diphenylphosphino)methyl-2-methylpropyl Acetate Ligand.CHEMINFORM, Issue 34 2010Syogo Ejiri Abstract The reaction is effective for the aromatic zinc derivatives bearing electron-withdrawing substituents, while poor yields are observed for the electron-donating and unsubstituted substrates [cf. [source] | ||||||||||