The simultaneous adsorption of SO2, NO, and CO2 on K2CO3‐modified γ‐alumina under different operating conditions was studied in a fixed‐bed reactor. The experimental results showed that the influence of a temperature increase on the simultaneous adsorption of the three gases was complex and different from the effects seen when both chemical adsorption and competitive adsorption existed. An increase in O2 concentration and small amounts of water could enhance the adsorption of SO2 and NO while the adsorption of CO2 was not influenced. The breakthrough curves of the simultaneous adsorption experiments suggested that the investigated adsorbent may be a good candidate for the simultaneous adsorption of SO2, NO, and part of the CO2 while the adsorption capacity for CO2 still needs to be enhanced. 相似文献
The highly catalytic asymmetric α‐hydroxylation of 1‐tetralone‐derived β‐keto esters and β‐keto amides using tert‐butyl hydroperoxide (TBHP) as the oxidant was realized by a chiral N,N′‐dioxide‐magnesium ditriflate [Mg(OTf)2] complex. A series of corresponding chiral α‐hydroxy dicarbonyl compounds was obtained in excellent yields (up to 99%) with excellent enantioselectivities (up to 98% ee). The products were easily transformed into useful building blocks and the precursor of daunomycin was achieved in an asymmetric catalytic way for the first time. 相似文献
In accordance with a novel strategy for generating the 2‐benzazepine scaffold by connecting C6–C1 and C3–N building blocks, a set of 5‐phenylsulfanyl‐ and 5‐benzyl‐substituted tetrahydro‐2‐benzazepines was synthesized and pharmacologically evaluated. Key steps of the synthesis were the Heck reaction, the Stetter reaction, a reductive cyclization, and the introduction of diverse N substituents at the end of the synthesis. High σ1 affinity was achieved for 2‐benzazepines with linear or branched alk(en)yl residues containing at least an n‐butyl substructure. The butyl‐ and 4‐fluorobenzyl‐substituted derivatives, (±)‐5‐benzyl‐2‐butyl‐2,3,4,5‐tetrahydro‐1H‐2‐benzazepine ( 19 b ) and (±)‐5‐benzyl‐2‐(4‐fluorobenzyl)‐2,3,4,5‐tetrahydro‐1H‐2‐benzazepine ( 19 m ), show high selectivity over more than 50 other relevant targets, including the σ2 subtype and various binding sites of the N‐methyl‐D ‐aspartate (NMDA) receptor. In the Irwin screen, 19 b and 19 m showed clean profiles without inducing considerable side effects. Compounds 19 b and 19 m did not reveal significant analgesic and cognition‐enhancing activity. Compound 19 m did not have any antidepressant‐like effects in mice. 相似文献
Starting from 2,5‐bisbenzyloxy‐4‐methyl‐benzaldehyd 2‐(3‐amino‐2‐acetyl‐but‐2‐enyl)‐5‐methyl[1,4]benzoquinones 9a—e are synthesized as model compounds in order to study the ambident reactivity of enaminones and quinones. Spontaneus cyclization of 9b—e in ethanol or acetic acid to 1‐aza‐spiro[4,5]deca‐2,7‐dien‐6,9‐dion 20b—e in good yield is observed. 6‐Hydroxy‐3‐acetyl‐quinoline 21 is obtained from 9a . In one case ( 9c ) 2‐acetyl‐3‐benzylamino‐7‐hydroxy‐naphthalene ( 17 ) was formed as by‐product. 9d in alkoholic perchloric acid leads to quinolinium salt 18 in low yield. 相似文献
Addition of lithiated methoxyallene 5 to literature‐known amino aldehyde 3 followed by ozonolysis provided syn‐configurated α‐hydroxy‐β‐amino ester 6 in moderate overall yield and with an ee of 90%. The predominant formation of syn‐compounds may be due to a chelate controlled addition step. 相似文献
The highly catalytic asymmetric α‐hydroxylation of β‐indanone esters and β‐indanone amides using peroxide as the oxidant was realized with a new C‐2′ substituted Cinchona alkaloid derivatives. The two enantiomers of α‐hydroxy‐β‐indanone esters could be obtained by simply changing the oxidant. This protocol allows a convenient access to the corresponding α‐hydroxy‐β‐indanone esters and α‐hydroxy‐β‐indanone amides with up to 99% yield and 98% ee.
We have previously shown that the β‐aminopeptidases BapA from Sphingosinicella xenopeptidilytica and DmpA from Ochrobactrum anthropi can catalyze reactions with non‐natural β3‐peptides and β3‐amino acid amides. Here we report that these exceptional enzymes are also able to utilize synthetic dipeptides with N‐terminal β2‐amino acid residues as substrates under aqueous conditions. The suitability of a β2‐peptide as a substrate for BapA or DmpA was strongly dependent on the size of the Cα substituent of the N‐terminal β2‐amino acid. BapA was shown to convert a diastereomeric mixture of the β2‐peptide H‐β2hPhe‐β2hAla‐OH, but did not act on diastereomerically pure β2,β3‐dipeptides containing an N‐terminal β2‐homoalanine. In contrast, DmpA was only active with the latter dipeptides as substrates. BapA‐catalyzed transformation of the diastereomeric mixture of H‐β2hPhe‐β2hAla‐OH proceeded along two highly S‐enantioselective reaction routes, one leading to substrate hydrolysis and the other to the synthesis of coupling products. The synthetic route predominated even at neutral pH. A rise in pH of three log units shifted the synthesis‐to‐hydrolysis ratio (vS/vH) further towards peptide formation. Because the equilibrium of the reaction lies on the side of hydrolysis, prolonged incubation resulted in the cleavage of all peptides that carried an N‐terminal β‐amino acid of S configuration. After completion of the enzymatic reaction, only the S enantiomer of β2‐homophenylalanine was detected (ee>99 % for H‐(S)‐β2‐hPhe‐OH, E>500); this confirmed the high enantioselectivity of the reaction. Our findings suggest interesting new applications of the enzymes BapA and DmpA for the production of enantiopure β2‐amino acids and the enantioselective coupling of N‐terminal β2‐amino acids to peptides.相似文献
The material behaviour of dominant elastic‐plastic, spherical γ‐Al2O3‐granules at compression until primary breakage has been experimentally studied. The influence of particle size and moisture content on the compression behaviour was also investigated. The mechanical properties of the granules can be determined using the recorded force‐displacement curves. Additionally, the specific fracture energy distribution and the distribution of the equivalent impact velocity at fracture can be derived from the force‐displacement curves. 相似文献
The enantioselective acylation of racemic diisopropyl α‐ and β‐hydroxyphosphonates by hydrolases in t‐butyl methyl ether with isopropenyl acetate as acyl donor is limited by the narrow substrate specificity of the enzymes. High enantiomeric excesses (up to 99%) were obtained for the acetates of (S)‐diisopropyl 1‐hydroxy‐(2‐thienyl)methyl‐, 1‐hydroxyethyl‐ and 1‐hydroxyhexylphosphonate and (R)‐diisopropyl 2‐hydroxypropylphosphonate. The hydrolysis of a variety of β‐chloroacetoxyphosphonates by the lipase from Candida cylindracea and protease subtilisin in a biphasic system gives (S)‐β‐hydroxyphosphonates (ee 51–92%) enantioselectively. (S)‐2‐Phenyl‐2‐hydroxyethyl‐ and (S)‐3‐methyl‐2‐hydroxybutylphosphonates (ee 96% and 99%, respectively) were transformed into (R)‐2‐aminophosphonic acids of the same ee. 相似文献
Highly efficient syntheses of indolo[2,1‐a]isoquinolines, indolo[2,1‐a][2]benzazepines, pyrrolo[2,1‐a]isoquinolines and pyrrolo[1,2‐a]benzazepines in excellent yields have been achieved by the intramolecular photochemical cross‐coupling reactions of 3‐acyl‐2‐halo‐N‐(ω‐arylalkyl)indoles and 2‐chloro‐N‐(ω‐arylalkyl)pyrrole‐3‐carbaldehydes in acetone. A new heterocyclic ring system – pyrrolo[1,2‐d][1,4]benzoxazepine – has also been constructed for the first time in this work by the photocyclization of 2‐chloro‐N‐(2‐phenoxyethyl)pyrrole‐3‐carbaldehyde. 相似文献
The reaction of primary 2,3‐allenols with iodine (I2) afforded 2,5‐dihydrofurans while that of readily available 1‐aryl or 1‐methyl substituted 2,3‐allenols with bromine (Br2), N‐bromosuccinimide (NBS), I2 or N‐iodosuccinimide (NIS) formed the not easily available but synthetically useful 3‐halo‐3‐alkenals and 2‐halo‐2‐alkenyl ketones with good selectivity and yields via a sequential electrophilic interaction of X+ with the allene moiety, 1,2‐aryl or 1,2‐proton shift, and H+ elimination process. 相似文献
The activation of C Cl bond of (Z)‐α‐chloroalkylidene‐β‐lactones and (E)‐α‐chloroalkylidene‐β‐lactams via the Suzuki cross‐coupling reaction is reported in this paper. Alkyl, heteroaromatic, substituted phenyl‐ and alkenylboronic acids can be coupled with a wide variety of α‐chloroalkylidene‐β‐lactones and β‐lactams in excellent yields within a short period of time. The cross‐coupling reaction of optically active substrates leads to the optically active compounds without racemization of the corresponding chiral center. 相似文献
A novel series of optically active molecules based on a 4‐(2‐(benzhydryloxy)ethyl)‐1‐((R)‐2‐hydroxy‐2‐phenylethyl)‐piperidin‐3‐ol template were developed. Depending on stereochemistry, the compounds exhibit various degrees of affinity for three dopamine, serotonin, and norepinephrine transporters. These molecules have the potential for treating several neurological disorders such as drug abuse, depression, and attention deficit hyperactivity disorder.
Efficient one‐step syntheses of α,β‐ and β,β‐dihaloenones were achieved by ruthenium(II)‐catalyzed reactions between cyclic or acyclic diazodicarbonyl compounds and oxalyl chloride or oxalyl bromide in moderate to good yields. This methodology offers several significant advantages, which include ease of handling, mild reaction conditions, one‐step reaction, and the use of an effective and non‐toxic catalyst. The synthesized compounds were further transformed into highly functionalized novel molecules bearing aromatic rings on the enone moiety using the Suzuki reaction.
Efficient methods for the direct arylation and deacylative arylation of β‐ketophosphonates with iodoarenes in presence of a copper(I) or a copper(II) salt as the catalysts have been developed. The corresponding α‐arylphosphonates were obtained in high yields. A tentative mechanism for the deacylative arylation reaction was proposed on the basis of the experimental data. 相似文献
γ‐Fluoro‐α, β‐unsaturated carboxylic esters 7a, 7b and 7d and 4‐fluoro‐4‐phenylbut‐3‐enoic ester ( 8 ) are obtained by two alternative pathways from 2‐fluoro aldehydes 5a—d , either by Horner—Wadsworth—Emmons reaction or by Wittig reaction. The aldehydes 5a—d are prepared by Swern oxidation of the corresponding fluorohydrins 4a—d . These are available from α‐olefins by bromofluorination, bromineby‐acetate replacement and subsequent hydrolysis. 相似文献