Showing papers on "Morpholine published in 2006"
TL;DR: The basic reaction pattern was extended to a catalytic enantioselective alkylative aldol reaction to ketones using dialkylzinc reagents as the initiator.
Abstract: A general catalytic asymmetric reductive aldol reaction of allenic esters to ketones is described. Two distinct constitutional isomers were selectively produced depending on the reaction conditions. A combination of CuOAc/(R)-DTBM-SEGPHOS/PCy3 as the catalyst predominantly produced γ-cis-products in high yield with excellent enantioselectivity (up to 99% ee). The reaction was applicable to both aromatic and aliphatic ketones, including unsaturated ketones. On the other hand, CuF−Taniaphos complexes produced α-aldol products with high diastereo- and enantioselectivity (up to 84% ee). The new Taniaphos derivative L3, containing di(3,5-xylyl)phosphine and morpholine units, produced optimum results in the α-selective reaction. The products are versatile chiral building blocks in organic synthesis. Furthermore, the basic reaction pattern (i.e., conjugate addition−aldol reaction) was extended to a catalytic enantioselective alkylative aldol reaction to ketones using dialkylzinc reagents as the initiator.
119 citations
TL;DR: The kinetics of the nucleophilic aromatic substitution of some 2-L-5-nitrothiophenes (para-like isomers) with three different amines with threeDifferent amines were studied in three room-temperature ionic liquids to gain information concerning reagent-solvent interactions.
Abstract: The kinetics of the nucleophilic aromatic substitution of some 2-L-5-nitrothiophenes (para-like isomers) with three different amines (pyrrolidine, piperidine, and morpholine) were studied in three room-temperature ionic liquids ([bmim][BF4], [bmim][PF6], and [bm(2)im][BF4], where bmim = 1-butyl-3-methylimidazolium and bm(2)im = 1-butyl-2,3-dimethylimidazolium). To calculate thermodynamic parameters, a useful instrument to gain information concerning reagent-solvent interactions, the reaction was carried out over the temperature range 293-313 K. The reaction occurs faster in ionic liquids than in conventional solvents (methanol, benzene), a dependence of rate constants on amine concentration similar to that observed in methanol, suggesting a parallel behavior. The above reaction also was studied with 2-bromo-3-nitrothiophene, an ortho-like derivative able to give peculiar intramolecular interactions in the transition state, which are strongly affected by the reaction medium.
85 citations
TL;DR: In this article, the reaction of acids, alcohols, acylamides, 1,2-diols, and amino alcohols with activated alkynes catalyzed by 1,4-diazabicyclo[2.2]octane (DABCO) was systematically investigated.
71 citations
TL;DR: N,O-Silyl dienyl ketene acetals derived from unsaturated morpholine amides have been developed as highly useful reagents for vinylogous aldol addition reactions with excellent enantioselectivity and high yields and selectivities obtained from aliphatic aldehydes.
Abstract: N,O-Silyl dienyl ketene acetals derived from unsaturated morpholine amides have been developed as highly useful reagents for vinylogous aldol addition reactions. In the presence of SiCl4 and the catalytic action of chiral phosphoramide (R,R)-3, N,O-silyl dienyl ketene acetal 8 undergoes high-yielding and highly site-selective addition to a wide variety of aldehydes with excellent enantioselectivity. Of particular note is the high yields and selectivities obtained from aliphatic aldehydes. Low catalyst loadings (2−5 mol %) can be employed. The morpholine amide serves as a useful precursor for further synthetic manipulation.
61 citations
TL;DR: In this paper, two morpholine-containing silicon (IV) phthalocyanines, namely bis (2-morpholine) ethoxy phthylocyaninatosilicon (2 ) and bis(2-( N -methylmorpholine)) diiodide (3 ), have been prepared.
55 citations
TL;DR: Hdride reduction of 4-imidoyl-1-(2- and 3-haloalkyl)azetidin-2-ones turned out to be an efficient and straightforward method for the preparation 2-substituted piperazines and 1,4-diazepanes.
Abstract: A high-yielding, asymmetric synthesis of novel 4-formyl-1-(2- and 3-haloalkyl)azetidin-2-ones was developed as valuable starting materials for the synthesis of different enantiomerically enriched bicyclic azetidin-2-ones, such as piperazine, morpholine, and 1,4-diazepane annulated β-lactam derivatives. Especially the hydride reduction of 4-imidoyl-1-(2- and 3-haloalkyl)azetidin-2-ones turned out to be an efficient and straightforward method for the preparation 2-substituted piperazines and 1,4-diazepanes.
50 citations
TL;DR: Enantiopure morpholine derivatives have been prepared by selenocyclofunctionalization of chiral 3-allyl-2-hydroxymethyl-substituted perhydro-1,3-benzoxazine derivatives by exploiting the structure of the substituent at C-2 and the substitution pattern of the double bond.
Abstract: Enantiopure morpholine derivatives have been prepared by selenocyclofunctionalization of chiral 3-allyl-2-hydroxymethyl-substituted perhydro-1,3-benzoxazine derivatives. The cyclization occurs in high yields and diastereoselection, although the temperature of the reaction and the structure of the substituent at C-2 and the substitution pattern of the double bond can modify the regio- and stereochemistry of the final products.
48 citations
TL;DR: Evaluated protocols showed that the premised cyclization of the corresponding 2-(allyloxymethyl)aziridines into 3,5-di(bromomethyl)morpholines only proceeded well for the N-neopentylmorpholine, which was subsequently transformed into a 3-oxa-7-thia-9-azabicyclo[3.3.1]nonane derivative.
Abstract: 1-tert-Butyl-2-(allyloxymethyl)aziridine has been transformed for the first time diastereoselectively into cis-3,5-di(bromomethyl)-4-tert-butylmorpholine via an electrophile-induced ring closure using bromine in dichloromethane. The latter morpholine has been used as a substrate for the synthesis of the corresponding 3,5-di(methoxymethyl)morpholine and 3,5-di(cyanomethyl)morpholine upon nucleophilic displacement of both bromo atoms. Further evaluation of this protocol toward the synthesis of 4-arylmethyl- and 4-alkylmethyl-3,5-di(bromomethyl)morpholines showed that the premised cyclization of the corresponding 2-(allyloxymethyl)aziridines into 3,5-di(bromomethyl)morpholines only proceeded well for the N-neopentylmorpholine, which was subsequently transformed into a 3-oxa-7-thia-9-azabicyclo[3.3.1]nonane derivative. Also, in some other cases, the desired 3,5-di(bromomethyl)morpholines were isolated in low yields and transformed into the corresponding 3,5-di(cyanomethyl)morpholines.
47 citations
TL;DR: In this paper, the solubility of methane and ethane in six physical solvents (diethylene, triethylene-, and tetraethylene-glycol dimethyl ethers) was reported.
Abstract: New data are reported for the solubility of methane and ethane in six physical solvents [diethylene-, triethylene-, and tetraethylene-glycol dimethyl ethers; triethylene glycol monobutyl ether; a mixture of poly(ethylene glycol) dimethyl ethers (PEGDME 250); and N-formyl morpholine (NFM)]. The solubility data were measured at 25 °C, 40 °C, and 60 °C and expressed in the form of Henry's law constants.
45 citations
TL;DR: In this article, the catalytic activity of a water-soluble Mn(salen)OAc complex in the epoxidation of alkenes and hydroxylation of alkanes was studied in acetonitrile, at room temperature, using sodium periodate as an oxygen source.
Abstract: The catalytic activity of a water-soluble Mn(salen)OAc complex in the epoxidation of alkenes and hydroxylation of alkanes was studied in acetonitrile, at room temperature, using sodium periodate as an oxygen source. The effect of various axial ligands as co-catalyst such as triethylamine, diethylamine, piperidine, 4-cyanopyridine, 2-methylpyridine, 4-methylpyridine, 4- tert -butylpyridine, 2-methylimidazole, pyrazine, quinalidine, morpholine, triphenylphosphine and dimethylformamide were investigated in the epoxidation of cyclooctene. Imidazole as a strong π-donor was the best axial ligand. The effect of different solvents was studied in the epoxidation of cyclooctene and CH 3 CN/H 2 O was chosen as solvent. The effect of the oxygen donors such as NaIO 4 , Bu 4 NIO 4 , KHSO 5 , H 2 O 2 , H 2 O 2 /urea, NaOCl and tert -BuOOH was also studied in the epoxidation of cyclooctene where NaIO 4 was selected as an oxygen donor.
42 citations
TL;DR: The synthesis of two enantiomerically pure iminosugars, analogues of 1-L-deoxynojirimycin (l-DNJ) and 1-D-deoxymannojirimYcin (DMJ) was achieved using cyclic sulfate substituted isoxazoline derivatives, resulting in six new nitrogen analogs of salacinol.
Abstract: The synthesis of two enantiomerically pure iminosugars, analogues of 1-L-deoxynojirimycin (l-DNJ) and 1-D-deoxymannojirimycin (DMJ), was achieved using cyclic sulfate substituted isoxazoline derivatives. The piperidine ring was formed via the reduction of an isoxazoline into an amine which underwent a spontaneous intramolecular cyclization by reaction with the cyclic sulfate moiety. The nucleophilic attack of these two trisubstituted piperidines and morpholine on L- and D-erythritol-1,3-cyclic sulfates gave six new nitrogen analogues of salacinol. The inhibitory properties of the synthesized salacinol analogues were evaluated on several commercial glycosidases.
TL;DR: In this paper, the Gewald reaction of aryl alkyl ketones with ethyl cyanoacetate and elemental sulfur in the presence of morpholinium acetate and excess morpholine was used to obtain 2-Aminothiophene-3-carboxylates.
Abstract: 2-Aminothiophene-3-carboxylates bearing various aryl groups at the 4-position are readily obtained in good to moderate yields by the one-pot Gewald reaction of aryl alkyl ketones with ethyl cyanoacetate and elemental sulfur in the presence of morpholinium acetate and excess morpholine.
TL;DR: A broad variety of chiral C/N-functionalized morpholine alcohols sharing a common structural motif in the 3-(hydroxymethyl)morpholine 6 were prepared from enantiomerically pure serine for the purpose of studying their catalytic ligand properties as discussed by the authors.
Abstract: A broad variety of chiral C/N-functionalized morpholine alcohols sharing a common structural motif in the 3-(hydroxymethyl)morpholine 6 were prepared from enantiomerically pure serine for the purpose of studying their catalytic ligand properties. The asymmetric addition of diethylzinc to benzaldehyde in the presence of 10 mol % of chiral C/N-functionalized morpholine alcohols gave 1-phenyl-1-propanol in 59–81% yield with 10–30% ee. The addition of 10 mol % of n -butyl lithium to the reaction mixture resulted in a significant enhancement of the stereoselectivity in the case of ligands bearing the two geminal phenyl substituents on the backbone. In the presence of n -butyl lithium and using ( S )-3-(hydroxydiphenylmethyl)morpholine ( S )- 19 as the chiral promoter, ( S )-1-phenyl-1-propanol was obtained in 81% yield with 76% ee. The geminal diphenyl-class of morpholine ligands was examined for the diethylzinc addition to four different aldehydes in the presence of n -butyl lithium. ( S )- N -Benzyl-3-(hydroxydiphenylmethyl)morpholine ( S )- 27 was found to be most enantioselective in the case of 4-methoxybenzaldehyde to give ( R )-alcohol in 87% yield with 80% ee. Catalysts ( S )- 19 and its N -methyl derivative ( S )- 26 gave alcohols with an ( S )-absolute configuration while the N-benzylated derivative ( S )- 27 gave the opposite enantiomeric products. The tentative transition state models to account for the observed product stereoselectivity with morpholine ligands holding the geminal diphenyl group on the β-amino alcohol segment are proposed.
Patent•
27 Oct 2006TL;DR: In this paper, the authors define a class of compounds that are identical with or different from each other are a hydrogen atom or a C1-C6 alkyl; X1 is an optionally substituted C1C6-alkylene; Xa is a methoxy group or fluorine atom; Xb is an oxygen atom or methylene group.
Abstract: Compounds of the formula: (I) [wherein R1, R2, R3 and R4 either identical with or different from each other are a hydrogen atom or a C1-C6 alkyl; X1 is an optionally substituted C1-C6 alkylene; Xa is a methoxy group or fluorine atom; Xb is an oxygen atom or methylene group (provided that when Xa is methoxy, Xb is limited to an oxygen atom); and Ar1 is an aryl, pyridinyl, aryloxy or pyridinyloxy, optionally having a substituent, such as a halogen atom], and pharmacologically acceptable salts thereof, and use thereof as pharmaceuticals.
TL;DR: In this paper, the secondary amine SA (dimethylamine DMA, diethylamine DEA, pyrrolidine Pyr, piperidine Pip, morpholine Mor) to pentafluoropropene PFP gives rise to generation of mixtures of two products (1-dialkylamine-1, 3,3,3-3, 3-tetrafluorOPropene and N,N-dialkyl-1.
TL;DR: This Letter describes the synthesis and SAR, developed through an iterative analog library approach, of potent and selective non-sarcosine-derived GlyT1 inhibitors.
TL;DR: Carbon dioxide solubility in 3.5 m morpholine, 17.7 m 2-aminoethoxyethanol (diglycolamine or DGA), and 3.6 m DGA was studied in this article.
Abstract: Carbon dioxide solubility was studied in 3.5 m (23.5 wt %) morpholine (MOR), 17.7 m (65 wt %) 2-aminoethoxyethanol (diglycolamine or DGA), and 3.6 m MOR + 14.7 m DGA (11 wt % MOR + 53 wt % DGA). CO...
TL;DR: The intramolecular cyclisation of heteroaryllithiums derived from N -heteroarylmethylpyrrole-2-carboxamides takes place smoothly at low temperature when N -methoxy- N -methyl and morpholine amides are used as internal electrophiles.
TL;DR: In this paper, the synthesis, derivatization and coordination behavior of N-diphenylphosphinomorpholine (1) and N-diaphinopiperazine (2) is described.
TL;DR: The photophysical properties of three photoinitiators with a covalently linked thioxanthone sensitizer unit absorbing up to 410nm were investigated by laser-flash photolysis and CIDNP spectroscopy.
Abstract: The photophysical properties of three photoinitiators with a covalently linked thioxanthone sensitizer unit absorbing up to 410 nm were investigated by laser-flash photolysis and CIDNP spectroscopy. These complementary techniques revealed two competing reaction pathways of the molecular dyads 1–3: i) triplet-energy transfer from the sensitizer to the morpholine moiety followed by α-cleavage to yield a radical pair, which initiates radical polymerization, and ii) bimolecular electron transfer from the morpholine to the thioxanthone subunit followed by proton transfer. The relative efficiency of these routes is determined by the triplet energy of the photoinitiator moiety relative to that of the sensitizer.
TL;DR: The complexes exhibit catalytic activity in the oxidation of benzyl alcohol to benzaldehyde in the presence of N-methyl morpholine-N-oxide (NMO) and an octahedral structure has been proposed for all of the complexes.
TL;DR: In this article, two vic-dioxime ligands (LxH2) containing morpholine group have been synthesized from 4-[2-(dimethylaminoethyl)] morpholine with anti-phenylchloroglyoxime or anti-monochlor glyoxime in absolute THF at −15 °C.
Abstract: Two vic-dioxime ligands (LxH2) containing morpholine group have been synthesized from 4-[2-(dimethylaminoethyl)] morpholine with anti-phenylchloroglyoxime or anti-monochloroglyoxime in absolute THF at −15 °C. Reaction of two vic-dioxime ligands with MCl2·nH2O (M: Ni, Cu or Co and n = 2 or 6) salts in 1:2 molar ratio afforded metal complexes of type [M(LxH)2] or [M(LxH)2·2H2O]. All of metal complexes are non-electrolytes as shown by their molar conductivities (Λm) in DMF (dimethyl formamide) at 10−3 mol·L−1. Structures of the ligands and metal complexes have been solved by elemental analyses, FT-IR, UV-Vis, 1H NMR and 13C NMR, magnetic susceptibility measurements, molar conductivity measurements. Furthermore, redox properties of the metal complexes were investigated by cyclic voltammetry.
TL;DR: The structure of 2-bromooreoselon, which was prepared by bromination of peucedanin or oreoselon with molecular bromine, was established as discussed by the authors.
Abstract: The structure of 2-bromooreoselon, which was prepared by bromination of peucedanin or oreoselon with molecular bromine, was established. The compositions and structures of the reaction products of this bromide with amines, such as pyridine, triethylamine, and morpholine, as well as with sodium acetate and potassium hydroxide were studied. The reaction of peucedanin with m-chloroperoxybenzoic acid affords peuruthenicin isobutyrate.
TL;DR: The ionic liquid-mediated ring opening can efficiently be carried out with aliphatic amines like morpholine as well and was completely regio- and stereoselective in each case.
TL;DR: Tri-tert-butoxysilanethiol reacts with secondary amines: diethylamine, morpholine, dicyclohexylamine and 2,2,4,4-tetramethylpiperidine yielding appropriate ammonium salts as discussed by the authors.
TL;DR: Benzenesulfinyl morpholine has been applied as a new promoter for the activation of thioglycosides and this reagent works well in the pre-activation one-pot oligosaccharide assembly strategy.
Abstract: Benzenesulfinyl morpholine (BSM) has been applied as a new promoter for the activation of thioglycosides. This proceeds by the in situ reaction of BSM with trifluoromethanesulfonic anhydride, which subsequently activates thioglycosides for glycosylations. Importantly, this reagent works well in our pre-activation one-pot oligosaccharide assembly strategy.
TL;DR: In this article, a series of 1,3,5,triaryl and 1,5-pentanediones was obtained via a sequential aldol condensation and Michael addition reaction in ionic liquid catalyzed by morpholine, as a one-pot reaction.
Patent•
15 Feb 2006
TL;DR: In this article, a preparation method of 4-(3-chlor-4-fluorobenzeneamidocyanogen)-7-methoxy-6-(3morpholine oxypropyl)quinazoline, which comprises using 3,4-dimethoxybenzoic acid as raw material, synthesizing 2-amido-4methoxoxy-5-hydroxybenzosic acid (V), cyclizing to obtain 6-hydrox-7methiox-3, 4-dihydroquinazolin-4
Abstract: The invention relates to a preparation method of 4-(3-chlor-4-fluorobenzeneamidocyanogen)-7-methoxy-6-(3-morpholine oxypropyl)quinazoline, which comprises using 3,4-dimethoxybenzoic acid (II) as raw material, synthesizing 2-amido-4-methoxy-5-hydroxybenzoic acid (V), cyclizing to obtain 6-hydroxy-7-methoxy-3,4-dihydroquinazolin-4-one (VI), directly chloridizing to obtain 4-chloro-hydroxy-7-methoxy-quinazoline (VII), reacting directly with 3-chloro-4-fluoroaniline, carrying out amination to obtain 4-(3-chloro-4-fluoroanilino)-6-hydroxy-7-methoxy-quinazoline (VIII), finally reacting with morpholinyl chloropropane to obtain Geftinat (I).
TL;DR: In this article, a cycloaddition to the central C-N bond of 3-phenyl-1-azabicyclo[1.1.0] butane is interpreted by a stepwise reaction mechanism via a relatively stable zwitterionic intermediate, which could be intercepted by morpholine to give a 1 : 1 :1 : 1 adduct 12, which undergoes a spontaneous elimination of HCN to yield the fumarate 13 (Scheme 4).
Abstract: The reactions of 3-phenyl-1-azabicyclo[1.1.0]butane (4) with dimethyl dicyanofumarate ((E)-8) and dimethyl dicyanomaleate ((Z)-8) lead to the same mixture of cis- and trans-4-phenyl-1-azabicyclo[2.1.1]-hexane 2,3-dicarboxylates (cis-11 and trans-11, resp.; Scheme 3). This result of a formal cycloaddition to the central C-N bond of 4 is interpreted by a stepwise reaction mechanism via a relatively stable zwitterionic intermediate 10, which could be intercepted by morpholine to give a 1 : 1 : 1 adduct 12, which undergoes a spontaneous elimination of HCN to yield the fumarate 13 (Scheme 4).
TL;DR: In this paper, the structure of a palladium-II acetate complex (C4H9ON)2Pd(OAc)2 · 2H2O (1) has been established by X-ray diffraction.
Abstract: Methods for the synthesis of new palladium(II) acetate complexes [L2Pd(OCOCH3)2], where L is N-coordinated morpholine (C4H9ON) or 4-methylmorpholine (C5H11ON), have been developed. The structure of the complex (C4H9ON)2Pd(OAc)2 · 2H2O (1) has been established by X-ray diffraction. The crystals of 1 are monoclinic (C12H26O8N2Pd, M = 434.76), space group P2(1)/c, a = 9.129(3) A, b = 16.227(5) A, c = 6.159(2) A, V = 878.5(5) A3, Z = 2. The palladium atom has a square-planar environment with the trans arrangement of ligands. The complex (C5H11ON)2Pd(OAc)2 (2) has a similar structure, according to spectroscopic data.