Acrylic Acid Derivatives Research Articles

Nitrogen-Containing Organofluorine Derivatives: An Overview

Fluorinated organic compounds, in particular those containingnitrogen atoms, are popular targets in medicinal chemistry. Theyare obtained through chemical synthesis, usually by employing small,fluorinated molecules as starting building blocks. This accountfocuses on the reactivity and synthetic applications of differenttypes of fluorinated building blocks. It summarizes recent methodologiesdeveloped in our and other laboratories for the synthesis of a varietyof nitrogen-containing organofluorine compounds. 1 Introduction 2 Fluorinated Imidoyl Halides 2.1 Reaction of Fluorinated Imidoyl Chlorides with Enolates: Synthesisof Fluorinated β-Amino Acids 2.2 Reaction of Fluorinated Imidoyl Chlorides with Sulfoxides 3 Fluorinated α-Imino Esters and Imines 3.1 Fluorinated α-Imino Esters 3.2 Fluorinated Aldimines and Ketimines 4 Fluorinated Acrylic Acid Derivatives 5 Fluorinated GEM-Difluoroalkynes 6 Fluorinated Nitriles 6.1 Synthesis of Fluorinated Uracils 6.2 Synthesis of Fluorinated Pyrimidin-2(1 H)-ones 7 Fluorinated β-Dicarbonylic Compounds 8 Miscellaneous 8.1 Tandem Ring-Closing Metathesis-Isomerization 8.2 β-Amino-α-trifluoromethyl Alcohols 9 Conclusion

Asymmetric 1,3-Dipolar Cycloaddition Reactions of Nitrile Oxides Catalyzed by Chiral Binaphthyldiimine-Ni(II) Complexes

Asymmetric cycloaddition reactions between several nitrile oxides and 3-(2-alkenoyl)-2-oxazolidinones and 2-(2-alkenoyl)-3-pyrazolidinone derivatives were carried out in the presence of chiral binaphthyldiimine (BINIM)-Ni(II) complexes as catalysts. Using (R)-BINIM-4(3,5-xylyl)-2QN-Ni(II) complex (30 mol %), good regioselectivity (4-Me/5-Me = 85:15) along with high enantioselectivity (96% ee) of the 4-Me adduct were obtained for the reaction between isolable 2,4,6-trimethylbenzonitrile oxide and 3-crotonoyl-5,5-dimethyl-2-oxazolidinone. Substituted and unsubstituted benzonitrile oxides and aliphatic nitrile oxides, which were generated from the corresponding hydroximoyl chloride in the presence of MS 4A, were reacted with 3-crotonoyl-5,5-dimethyl-2-oxazolidinone, 5,5-dimethyl-3-(2-pentenoyl)-2-oxazolidinone, 5,5-dimethy-3-[3-(ethoxycarbonyl)propenoyl]-2-oxazolidinone, 1-benzyl-2-crotonoyl-5,5-dimethyl-3-pyrazolidinone, and 1-benzyl-2-[3-(ethoxycarbonyl)propenoyl]-5,5-dimethy-3-pyrazolidinone in the presence of (R)-BINIM-4Ph-2QN-Ni(II) or (R)-BINIM-4(3,5-xylyl)-2QN-Ni(II) complexes (10-30 mol %) as catalysts to give the corresponding cycloadducts in high yields, with high regioselectively (4-R/5-R = 85:15-99:1) and with moderate to high enantioselectivities (42-95% ee) of the 4-R adducts. Higher enantioselectivities and regioselectivities were obtained for the reactions using pyrazolidinone derivatives as the dipolarophiles. For the cycloadditions of 2-(2-alkenoyl)-1-benzyl-5,5-dimethyl-3-pyrazolidinones catalyzed by (R)-BINIM-4(3,5-xylyl)-2QN-Ni(II) complex (30 mol %), the enantioselectivity varied from 75% to 95% ee. The reactions between several nitrile oxides and 2-acryloyl-1-benzyl-5,5-dimethyl-3-pyrazolidinone in the presence of (R)-BINIM-4(3,5-xylyl)-2QN-Ni(II) complex (10 mol %) resulted in enantioselectivities (79-91% ee) that exceed those of previously reported enantioselective cycloadditions of acrylic acid derivatives. Furthermore, studies using a molecular modeling program using PM3 calculations were carried out to gain insight into the mechanisms of the asymmetric induction.

ChemInform Abstract: Enantioselective Organocatalytic Michael Additions to Acrylic Acid Derivatives: Generation of All‐Carbon Quaternary Stereocenters.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A Selective and Practical Synthesis of Nitroolefins

AbstractA straightforward and general synthesis of nitroolefins from nitric oxide (NO) and olefins is presented. The direct nitration of aromatic olefins, allyl compounds, and acrylic acid derivatives proceeds smoothly at room temperature with high regioselectivity and good yields. The advantages of this novel procedure compared to established nitration procedures are demonstrated.

Nanocrystal Fabrication of Acrylic Acid Derivatives with a Long-Alkyl Group and Their Solid-State Polymerization

Nanocrystals of octadecyl acrylate 1 , octadecyl methacrylate 2 and N-octadecylacrylamide 3 were prepared by the reprecipitation method as water dispersion for the first time. Their sizes were from 120 nm to 350 nm depending on the preparation conditions. Although polymerization of 1 through 3 in nanocrystals was essentially the same as that in bulk crystals, it is interesting that 1 showed smaller average molecular weight and dispersity index in nanocrystals compared with in the bulk crystals.

PH-sensitive polymers for cytoplasmic drug delivery

The pH-sensitive drug delivery systems could be triggered by a mild acidic environment, such as that occurring in solid tumors, inflammatory tissues and intracellular endosomal compartments. Moreover, the cytoplasmic delivery of internalized macromolecules (such as oligonucleic acid, siRNA, DNA, proteins and polymer–antibody complex) will be possible. Synthetic polymers – such as polyanions (acrylic acid derivatives) and polycations (poly ethylenimine and chitosan complexes) – are among the most popular compounds studied for intracellular trafficking of drugs. As research is progressing in the area of cytoplasmic delivery, many novel and innovative applications making use of the unique properties of pH-sensitive polymers are expected in the future.

Preparation of polymer electrolyte membranes consisting of alkyl sulfonic acid for a fuel cell using radiation grafting and subsequent substitution/elimination reactions

Polymer electrolyte membranes (PEMs) consisting of alkylsulfonic acid were successfully synthesized by radiation-induced graft polymerization of methyl acrylate (MA) into a poly(ethylene- co-tetrafluoroethylene) (ETFE) film, followed by sulfonation at an α-carbonyl carbon of the MA units in the grafting chain using an equimolar complex of chlorosulfonic acid and dioxane (ClSO 3H-complex). Sulfonation reaction with ClSO 3H-complex in the grafted chains of acrylic acid derivatives (acrylic acid and N, N-dimethylacrylamide) other than MA in the film could not be performed. The ion-exchange capacity (IEC) and ion conductivity of the MA-grafted PEM were controlled in the respective ranges of 0.54–1.47 mmol/g and 0.014–0.14 S/cm by changing the grafting degree. It has been confirmed by titrimetric and gravimetric analyses of sulfonic and carboxylic acids in the film that the sulfonation reaction is accompanied with decarboxylation of the MA units equimolar to the substituted sulfonic acids (substitution of carboxylic acid with sulfonic acid), and that the sulfonation degree was ca. 30%.

Eugenol functionalized poly(acrylic acid) derivatives in the formation of glass-ionomer cements

Eugenol possesses analgesic and anti-inflammatory properties with the ability to relieve pain in irritated or diseased tooth pulp, thus, incorporating polymers with eugenol moieties in dental cements is attractive. An acrylic derivative of eugenyl methacrylate (EgMA) was copolymerized with acrylic acid (AA) using a radical initiator, to yield a water soluble copolymer of acrylic acid and eugenyl methacrylate {p(AA-co-EgMA)}, which was then applied in the formulation of glass-ionomer cements for potential application as dental cements. Three concentrations of the p(AA-co-EgMA) copolymer in water were studied by, 30 wt%, 40 wt% and 50 wt%, and used with different powder:liquid ratios to formulate the glass-ionomer cements. The setting kinetics showed that both the concentration of the copolymer and the powder:liquid ratio influenced the working and setting times. Thus, selected formulations were used for further characterization of their mechanical properties, water uptake and fluoride release, to optimize the cement formulation. The experimental glass-ionomer cements exhibited physical and mechanical properties in compliance to ISO standard requirements with the benefit of the initial pH being greater than the commercial formulation used as the standard cement. Furthermore, the presence of the eugenyl moieties bound to the polymer matrix was advantageous with respect to moisture sensitivity and anti-bacterial properties.

ChemInform Abstract: Palladium/Phosphite‐Catalyzed 1,4‐Addition of Arylboronic Acids to Acrylic Acid Derivatives.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Template-Induced Enantioselectivity in the Reductive Radical Cyclization of 3-(3-Iodopropoxy)propenoic Acid Derivatives Depending on the Binding Motif

Different binding motifs HXC=O have been screened in the enantioselective radical cyclization of various linear derivatives of 3-(3-iodopropoxy)propenoic acid. The reactions were performed in the presence of an enantiomerically pure, chiral 1,5,7-trimethyl-3-azabicyclo[3.3.1]nonan-2-one derivative, which acts as a hydrogen-binding template. The cyclized products were obtained in good to excellent yields (66-88%). Enantioselectivities up to 59% ee were achieved.

Homo- and heterogeneous Ru-based metathesis catalysts in cross-metathesis of 15-allylestrone—towards 17β-hydroxysteroid dehydrogenase type 1 inhibitors

The cross-metathesis of allylestrone with acrylic acid derivatives using homogeneous and heterogenized Ru-catalysts was evaluated for the synthesis of a new 17β-hydroxysteroid dehydrogenase type 1 inhibitor. Hoveyda-type catalyst containing an additional diethylamino group turned out to be comparably active as homogeneous Grubbs II catalyst after immobilization on an acidic ion exchange resin which greatly facilitated workup.

Palladium-Catalyzed Synthesis of 3-Indolecarboxylic Acid Derivatives

Indoles having an ester functionality in the 3-position were prepared from 2-(2-nitrophenyl)propenoic acid derivatives via a palladium-catalyzed reductive N-heteroannulation using carbon monoxide as the ultimate reducing agent. The starting materials were prepared either by a Stille coupling of 2-halo-1-nitrobenzenes with ethyl 2-(tributylstannyl)-2-propenoate or by vicarious nucleophilic substitution of nitrobenzenes followed by a Knoevenagel-type condensation with an aldehyde. Synthesis of an example of a 3-nitrile- and a 3-sulfone-substituted indole is also described using the same type of methodologies.

ChemInform Abstract: Solvent‐Free Microwave‐Assisted ortho‐Alkylation of Aromatic Ketimine with Acrylic Acid Derivatives by Rh(I) Catalyst.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Palladium/Phosphite-Catalyzed 1,4-Addition of Arylboronic Acids to Acrylic Acid Derivatives

1,4-Addition of arylboronic acids to acrylic acid derivatives proceeds efficiently in the presence of a palladium catalyst system of Pd(OAc)2/(PhO)3P to produce the corresponding 3-arylpropionic acid derivatives. The use of the phosphite ligand is the key to conducting the addition smoothly with suppressing the competing Mizoroki-Heck-type oxidative coupling.

Enantioselective organocatalytic Michael additions to acrylic acid derivatives: generation of all-carbon quaternary stereocentres

Acrylic esters, thioesters and N-acryloyl pyrrole have been identified as effective electrophiles in the enantioselective Michael addition reaction with beta-keto ester pro-nucleophiles catalysed by a cinchona alkaloid derived bifunctional organocatalyst; enantiomeric excesses of up to 98% and yields of up to 96% can be obtained for a range of Michael acceptors and pro-nucleophiles.

The Mizoroki-Heck reaction in organic and aqueous solvents promoted by a polymer-supported Kaiser oxime-derived palladacycle

A polystyrene-supported palladacycle derived from Kaiser oxime resin 3 is examined in organic and aqueous media used for the Mizoroki-Heck reactions. The couplings are efficiently performed in the presence of polymeric palladacycles in DMF, aqueous DMA, or water at relatively moderate temperature (110-130 oC) similarly to that in the presence of dimeric 4- hydroxyacetophenone 6 and 4-nitrobenzophenone oxime 2 palladacycles. Different acrylic, crotonic, and cinnamic acid derivatives as well as styrenes are arylated with aryl iodides, bromides, and chlorides with high efficiency. Enone precursors of 4-(p-hydroxyphenyl) and 4- (p-methoxy)phenylbutan-2-one, which are natural odorous products extracted from Aloe wood with raspberry scent, have been prepared by arylation of methyl vinyl ketone. Methylated resveratrol and the anti-cancer agent DMU-212 ((E)-3,4,5,4'-tetramethoxystilbene) have been prepared in high yields. Related Mizoroki-Heck reactions of o-halobenzaldehydes and o- iodoaniline with tolane afforded indenone and indol derivatives, respectively. XPS analysis of the starting and recycled polymer indicated that contains exclusively Pd(II). In addition, poisoning studies with Hg(0) of the reaction mixture stop the process indicating that the palladacycle acts as source of Pd(0) species. Recycling experiments are performed in organic and aqueous solvents with relatively low palladium leaching from the polymer (0.4-5% in DMF and 2-2.7% in H2O). ICP-OES analyses also indicate very low levels of Pd in the isolated crude products (2.9-37.2 ppm).

Synthesis of 2‐(9‐Fluorenyl)acrylic Acid Derivatives via Intramolecular Friedel—Crafts Reaction of Morita—Baylis—Hillman Adducts of 2‐Biphenylcarboxaldehydes.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Solvent-free Microwave-Assisted Ortho-Alkylation of Aromatic Ketimine with Acrylic Acid Derivatives by Rh(I) Catalyst

The article reports the synthesis of a novel bispyridino-18-crown-6 ether, 7-{[(5S,15S)-5,15-diphenyl- 3,6,14,17-tetraoxa-23,24-diazatricyclo[17.3.1.18,12]tetracosa-1(23),8(24),9,11,19,21-hexaen-10-yl]oxy}heptylferrocenamide 6, bearing the C2-symmetric diphenyl substituents as chiral barriers and the ferrocenyl groups serving as an electrochemical sensor, and its electrochemical study with D- and L-AlaOMe·HCl as the guest by cyclovoltametry.

Photoinduced Diastereoselective Addition of Perfluoroalkyl Iodides to Acrylic Acid Derivatives for the Synthesis of Fluorinated Amino Acids.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Hydrogenation of unsaturated carboxylic acids on functional gel-type resin supported Pd catalysts: The effect of reactant structure

Functional gel-type resin-based palladium catalysts (0.5–2 wt.% Pd) of well dispersed Pd nanoparticles were prepared and characterized by SEM, TEM techniques and swelling measurements. The role of specific properties of gel-type matrix was studied in the hydrogenation of unsaturated C C bonds in series of carboxylic acids, derivatives of acrylic acid. They differ in the type of substituents (methyl, phenyl and carboxyl groups) at the double bonded carbon atoms. The rate of hydrogenation is found to depend on the crosslinking degree of the resin and on the presence of steric hindrance around the C C bond in individual reactants. The influence of the substrate molecules size, their hydrophobicity and absolute hardness/polarizability on the rate of the C C hydrogenation has been established by theoretical modelling.