Vinyloge Acylverbindungen. XX. Reaktivität und Toxizität arylsubstituierter β-Chlorvinylketone, β-Chlorvinylaldehyde und β-Chlorvinylmethyleniminiumsalze

Vinylogous Acyl Compounds. XX. Reactivity and Toxicity of Aryl-substituted β-Chlorovinyl Ketones, β-Chlorovinyl Aldehydes, and β-Chlorovinyl Methyleniminium Salts Based on kinetic measurements, the nucleophilic replaceability of the chlorine in aromatic β-chlorovinyl ketones ArCO-CH  CH-Cl ( 1 ), isomeric β-chlorovinyl aldehydes OCH CHC(Cl)Ar( 2 ), and corresponding β-chlorovinyl methyleniminium salts Me₂N^⊕;CH CHC(Cl)Ar X^⊖ ( 3 ) is compared and related to toxicological findings. The chemical reactivity of these important synthetic building blocks increases in the order 2 < 1 < 3 , the acute toxicity (24 h LD₅₀ i. p. in the mouse) shows the graduation 2 < 3 < 1 . Compounds of type 1 prove to be relatively toxic (LD₅₀ 24–42 mg/kg) and display a marked necrotic action after percutaneous absorption, whereas the aldehydes 2 have not only a minor acute toxicity (LD₅₀ 158–298 mg/kg) but also a somewhat less marked skin damaging activity. In addition, the LD₅₀ values of selected β-chlorovinyl carbonyl compounds are compared with those of corresponding halogen-free compounds as well as of vinylogous carbonamidium salts ArCO CHCH N^⊕R₃X^⊖. The latter, which can be used as synthetic equivalents of 1 , differ in both the reduced acute toxicity and missing skin damaging properties.     

Chelation of chitosan derivatives with zinc ions. II. Association complexes of Zn2+ onto O,N‐carboxymethyl chitosan

The chelation of zinc ions onto O,N‐carboxymethyl chitosan (ONCMCh) was characterized using a Fourier transform infrared (FTIR) spectrophotometer and a scanning electron microscope (SEM). From the FTIR spectra, little change in the absorption intensities and frequencies at 3300–3600 cm⁻¹ of Zn²⁺ ONCMCh chelated specimens suggested that  OH and  NH₂ groups were not participating in the chelation reaction. The absence of absorption bands at 1755–1700 cm⁻¹ suggested that the carboxyl group CO was not ionized, and the ionized CO bands were observed at 1400–1600 cm⁻¹ for chelated specimens. Thus, the chelation sites took place at the carboxyl group rather than at the  OH and NH₂ groups. It also confirmed that water‐insoluble chelates, which were formed through the Zn O and Zn N bonds, presented a tetrahedral structure. The water‐soluble complexes where zinc ions connected with oxygen of CO and water molecules were only due to electron attraction. Formation of different microstructures on the surfaces, as revealed by SEM, provided evidence to distinguish different chelating mechanisms between water‐soluble and water‐insoluble complexes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1476–1485, 2001     

Phosphorus-Containing polyurethanes based on bisphenol-AF,prepared by N-alkylation

Phosphorus-containing polyurethanes (PU-P) based on bisphenol-AF were synthesized by N-alkylation in a two-step process. First, the polymer was metalated with sodium hydride; then the prepared urethane polyanion was treated with diethyl 2-bromoethyl phosphate. IR spectra exhibited characteristic absorptions at 1303 cm⁻¹ (PO stretch), 1015 cm⁻¹ (CH stretch), 1646 cm⁻¹ (CO stretch), 1231 cm⁻¹ (CNH), and 1053 cm⁻¹ (CO O C stretch). In the ¹H-NMR spectrum of the maximum substituted PU-P, the signal of the urethane proton (NH  CO O) at 9.87 ppm virtually disappeared as expected; new signals appeared at 1.20–1.24 ppm (POCH₂CH ₃) and 3.79 ppm (POCH ₂CH₃). Physical and thermal properties of the N-alkylated polymer were also investigated with differential scanning calorimetry (DSC), solubility, X-ray diffraction, thermogravimetric analysis (TGA), limiting oxygen index (LOI), and reduced viscosity. DSC analysis showed that T_g values were decreased from 81 to 43°C. The reduced viscosities of the PU-Ps were observed in the range of 0.23–0.18 dL g⁻¹. The results of TGA revealed that the thermal stability was decreased, because the phosphorus moiety in the PUs is readily dissociated thermally. The PU-Ps exhibited enhanced fire resistance because phosphorus simultaneously promoted carbonization of the polymer and inhibited combustion. The X-ray diffraction patterns of the PU-Ps showed that with increasing phosphorus content, the degree of crystallinity of the PUs decreased. N-alkylated PUs are soluble, not only in polar solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and H₂SO₄, but also in less polar solvents such as phenol, toluene, THF, and trichloroethylene. © 1996 John Wiley & Sons, Inc.     

A Novel Class of N-Sulfonyl and N-Sulfamoyl Noscapine Derivatives that Promote Mitotic Arrest in Cancer Cells

Noscapine displays weak anticancer efficacy and numerous research efforts have attempted to generate more potent noscapine analogues. These modifications included the replacement of the N-methyl group in the 6′-position with a range of substituents, where N-ethylcarbamoyl substitution was observed to possess enhanced anticancer activity. Herein, we describe advances in this area, namely the synthesis and pharmacological evaluation of a series of N-sulfonyl and N-sulfamoyl noscapine derivatives. A number of these sulfonyl-containing noscapinoids demonstrated improved activities compared to noscapine. ((R)-5-((S)-4,5-Dimethoxy-1,3-dihydroisobenzofuran-1-yl)-4-methoxy-6-((1-methyl-1H-imidazol-4-yl)sulfonyl)-5,6,7,8-tetrahydro[1,3]dioxolo[4,5-g]isoquinoline) ( 14 q ) displayed sub-micromolar activities of 560, 980, 271 and 443 nM against MCF-7, PANC-1, MDA-MB-435 and SK-MEL-5 cells, respectively. This antiproliferative effect was also maintained against drug-resistant NCI/Adr^RES cells despite high expression of the multidrug efflux pump, P-glycoprotein.     

Aza-enamine. IV. Nachweis des Enamin-Charakters von N,N-alkylsubstituierten Aldehydhydrazonen anhand NMR- und UV-spektroskopischer Untersuchungen

Aza-enamines. IV. Proof of Enamine Character of N,N-Alkylated Hydrazones Given by N.M.R.- and U.V.-Spectroscopy Hydrazones of the type R¹ CH  N R² with R¹ = p-methoxyphenyl-, 1 , phenyl-, 2 , p-nitrophenyl-, 3 , ethyl-, 4 and R² = morpholino-, a , piperidino-, b , dimethylamino-, c , pyrrolidino-, d and dicyclohexylamino-, e have been investigated with regard to spectroscopic analogy to enamines. The conclusion has been drawn that aldehydehydrazones act similar enamines.     

d-NMR-Untersuchung der behinderten Rotation am -Bindungsinkrement. X. N-substituierte Thiocarbamidsäure-O-phenyl- und S-äthylester

d-N.M.R.-Investigation of the Restricted Rotation at the -Bonding Increment. X. N-Substituted Thiocarbamic acid-O-Phenyl- and S-Ethylesters The free enthalpies of activation of the restricted rotation at the partial -double bond in thiocarbamic acid esters have been determined for (R¹ = methallyl; R² = me, et, iso-pr, cycl. hex; X  S and Y  O C₆H₅ respectively X  O and Y  S C₂H₅). The results have been compared with values, earlier observed for other mono- and dithiocarbamic acid esters, substituted at nitrogen analogously.     

Organische Phosphorverbindungen. XIII. Reaktion vinyloger Chlormethylenimmoniumsalze mit Phosphorigsäuretrialkylestern

Organic Phosphorus Compounds. XIII. Reaction of Vinylogous Chloromethylene Immonium Salts with Trialkyl Phosphites 3-Chloropropenylidene immonium salts of the type Cl CArCH CHNMe₂^⊕X^⊖ don't react like chloromethylene immonium salts Cl CHNMe₂^⊕X^⊖ with trialkyl phosphites according to the classical MICHAELIS -ARBUSOV principle (RO)₃P + R′Cl → (RO)₂P(O)R′ + RCl but lead to salts of 1-dimethylaminophosphonates (RO)₂P(O) CH(NMe₂ · HX) CHCClAr the structure of which is confirmed by two independent syntheses. Some characteristic reactions of the free dimethylaminophosphonates are described.     

An Efficient Synthesis of Fused Polycyclic Triazolo[4,5-a]acridine Derivatives under Catalyst-Free Conditions with High Regioselectivity

An efficient synthesis of fused polycyclic 11-aryl-7,8,9,11-tetrahydro-1H-[1,2,3] triazolo[4,5-a]acridin-10(6H)-one derivatives is described in EtOH with high regioselectivity. This new procedure includes a three-component reaction of benzaldehyde, 1H-benzo[d] [1,2,3]triazol-5-amine and cyclohexane-1,3-dione under catalyst-free conditions, and has the advantages of one-pot reaction, milder reaction conditions, high yields and high regioselectivity.     

Facile,Efficient Copolymerization of Ethylene with Bicyclic,Non‐Conjugated Dienes by Titanium Complexes Bearing Bis(β‐Enaminoketonato) Ligands

Copolymerizations of ethylene with 5‐vinyl‐2‐norbornene or 5‐ethylidene‐2‐norbornene under the action of various titanium complexes bearing bis(β‐enaminoketonato) chelate ligands of the type, [R¹NC(R²)CHC(R³)O]₂TiCl₂ ( 1 , R¹=Ph, R²=CF₃, R³=Ph; 2 , R¹=C₆H₄F‐p, R²=CF₃, R³=Ph; 3 , R¹=Ph, R²=CF₃, R³=t‐Bu; 4 , R¹=C₆H₄F‐p, R²=CF₃, R³=t‐Bu; 5 , R¹=Ph, R²=CH₃, R³=CF₃; 6 , R¹=C₆H₄F‐p, R²=CH₃, R³=CF₃), have been shown to occur with the regioselective insertion of the endocyclic double bond of the monomer into the copolymer chain, leaving the exocyclic vinyl double bond as a pendant unsaturation. The ligand modification strongly affects the copolymerization behaviour. High catalytic activities and efficient co‐monomer incorporation can be easily obtained by optimizing the catalyst structures and polymerization conditions.     

Kinetics of the cyclization and isomerization reactions in polyacrylonitrile based carbon fiber precursors during thermal-oxidative stabilization

The kinetics of reactions in polyacrylonitrile (PAN) based carbon fiber (CF) production should be of significance to the guidance of process control, fiber structure formation. PAN precursor fibers were isothermally stabilized at 210, 225, 240, 255, and 270 °C, respectively, for 10 to 100 min in an air oven to study the kinetics of the cyclization and isomerization reactions. The structural evolution of PAN precursor fibers during thermal-oxidative stabilization was characterized by Fourier transform infrared (FTIR) spectroscopy and solid state ¹³C nuclear magnetic resonance (¹³C NMR). The results indicate that the FTIR absorbance of  CN (the resultant of the cyclization) in PAN shows a trend of first increasing and then decreasing. And then the NMR peak assigned to the carbon atoms linking imino groups ( NH ) proves the isomerization of  CN into  NH in pyridone structure. Based upon the FTIR absorbance method, the entire process of the cyclization and isomerization reactions is considered as a consecutive first-order reaction. A kinetic model for the consecutive reaction has been established via the evaluation of the reaction rate constants of two single reactions. According to the model, the simulated kinetic curves of the characteristic groups ( CN,  CN , and  NH ) conform to the FTIR absorbance trends of these groups based on experimental data. This study is expected to furnish in-depth information on the crucial reaction kinetics during stabilization of PAN precursors, which is of advantage to the process optimization of the CF production. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48819.     

Rhodium(III)‐Catalyzed in situ Oxidizing Directing Group‐ Assisted C?H Bond Activation and Olefination: A Route to 2‐Vinylanilines

A new and efficient method for the synthesis of 2‐vinylanilines from the reaction of arylhydrazine hydrochlorides with alkenes and diethyl ketone via a rhodium‐catalyzed C H activation is described. The oxidant‐free olefination reaction involves the in situ generation of an  N NCR¹R² moiety as the oxidizing directing group thus providing an easy access to 2‐vinylanilines.

     

Rhodium(II)‐Catalyzed Carbenoid Insertion of N‐Tosylhydrazones into Amide N?H Bonds: An Efficient Approach to N3‐Benzyl/Alkyl‐2‐arylquinazolinones

Dirhodium(II) acetate‐catalyzed reactions of N‐tosylhydrazones with dihydroquinazolinones bearing different types of N H bonds that give N³‐benzyl/alkyl‐2‐arylquinazolin‐4(3H)‐ones through Csp³ N bond formation by oxidative dehydrogenation and insertion of rhodium‐carbenoid into amide N H bond are reported for the first time. This method features good to excellent yields, good functional group tolerance, high regioselectivity and readily available starting materials.

     

Potassium Iodide/tert‐Butyl Hydroperoxide‐Mediated Oxidative Annulation for the Selective Synthesis of N‐Substituted 1,2,3‐Benzotriazine‐4(3H)‐ones Using Nitromethane as the Nitrogen Synthon

A novel and efficient oxidative annulation of 2‐aminobenzamides with nitromethane has been developed for the chemoselective synthesis of N‐substituted 1,2,3‐benzotriazine‐4(3H)‐ones in moderate to excellent yields under transition metal‐free conditions. Two N N bonds were constructed in one pot via C N cleavage of nitromethane, which was selectively employed as the nitrogen synthon. The preliminary mechanistic studies revealed that this protocol proceeded under hypoiodite catalysis generated in situ.

     

Iron‐Catalyzed C?C Bond Cleavage and C?N Bond Formation

A novel approach for C N bond formation was developed by iron‐catalyzed C C bond cleavage. Anilines and sulfonamides reacted smoothly with 2‐substituted 1,3‐diphenylpropane‐1,3‐diones to afford N‐alkylation products, in which the 1,3‐dicarbonyl group acts as a leaving group in the presence of an iron catalyst. The reversible C C bond cleavage plays a driving force to give the thermodynamically stable products. The method is complementary to the previous methods for C N bond formation.     

Vinyl‐addition copolymerization of norbornene and polar norbornene derivatives using novel bis(β‐ketoamino)Ni(II)/B(C6F5)3/AlEt3 catalytic systems

Copolymerization of norbornene (NBE) and polar norbornene derivatives undergoes vinyl polymerization by using novel catalyst systems formed in situ by combining bis(β‐ketoamino)Ni(II) complexes {Ni[R₁C(O)CHC(NR₃)R₂]₂ (R_l = R₂ = CH₃, R₃ = naphthyl, 1 ; R₁ = R₂ = CH₃, R₃ = C₆H₅, 2 ; R₁ = C₆H₅, R₂ = CH₃, R₃ = naphthyl, 3 ; R_l = R₂ = CH₃, R₃ = 2, 6‐(CH₃)₂C₆H₃, 4 ; R₁ = R₂ = CH₃, R₃ = 2, 6‐′Pr₂C₆H₃ 5 ; R₁ = C₆H₅, R₂ = CH₃, R₃ = 2, 6‐′Pr₂C₆H₃, 6 )} and B(C₆F₅)₃/AlEt₃ in toluene. The 1 /B(C₆F₅)₃/AlEt₃ catalytic system is effective for copolymerization of NBE with NBE OCOCH₃ and NBE CH₂OH, respectively, and copolymerization activity is followed in the order of NBE CH₂OH > NBE OCOCH₃ > NBE CN. The molecular weights of the obtained poly(NBE/NBE CH₂OH) reached 5.97 × 10⁴ to 2.07 × 10⁵ g/mol and the NBE CH₂OH incorporation ratios reached 7.0–55.4 mol % by adjusting the comonomer feedstock composition. The copolymerization of NBE and NBE CH₂OH also depend on catalyst structures and activity of catalyst followed in the order of 2 > 1 > 3 > 5 > 4 > 6 . The molecular weights and NBE CH₂OH incorporation ratios of poly(NBE/NBE CH₂OH) were adjustable to be 1.91–5.37 × 10⁵ g/mol and 9.5–41.1 mol %  OH units by using catalysts 1 – 6 . The achieved copolymers were confirmed to be vinyl‐addition type, noncrystalline and have good thermal stability (T_d = 380–410°C). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Zur Kupplung von 4-substituierten 2-Pyrazolin-5-onen mit p-Chinondiiminkationen; Nachweis isokinetischer Beziehungen

On the Coupling of 4-Substituted 2-Pyrazoline-5-ones with Quinone Diimine Cations; Detection of Isokinetic Relations The temperature dependence of the rate constant k_K of the coupling reaction between pyrazoline-5-ones 1a – i and quinone diimine cations 2a , b is determined in dependence of the substituents at the coupling position (R³:  H,  NN Ar, CHAr–pyrazoline-5-one). The activation enthalpies are between 7 and 60 kJ mol⁻¹ and the activation entropies between −132 and −19 J mol⁻¹ K⁻¹. An isokinetic relation with β = 106°C is found and a rate determining combination of the carbanions of 1a – i with 2a , b is proposed. Contrary to this, the 2-pyrazolin-5-ones 1j – l , n (R³:  S CNH₂NR) obey an isokinetic relation with β = −45°C. Taking into consideration the activation parameters, the low dependence of k_K on the ionic strength, and the decrease of k_K with the increase of the pK values of the couplers, a rate determining splitting off of R³ is assumed.     

Über die strukturanalystische Anwendung von „anomalen”︁ Multipletts in off-resonance entkoppelten 13C-NMR-Spektren von ?CH  CH?Fragmenten

On the Structural Analytical Application of „Anomalous”︁ Multiplets in Off-resonance Decoupled ¹³C NMR Spectra of  CH  CH Fragments The theoretical background of “anomalous” splitting of signals of molcular fragments  CHCH in off-resonance decoupled ¹³C NMR spectra is described. The use of these splitting phenomena on the determination of vicinal H,H and geminal C,H coupling constants is demonstrated using simple examples. The possibilities to determine the configuration of double bonds are shown by other examples from the field of natural constituents chemistry.     

Highly Stereoselective Synthesis of Arylene‐Silylene‐Vinylene Polymers

Stereoregular trans‐arylene‐silylene‐vinylene polymers of M_w=13100–34800 and PDI=1.6–2.9 of the general formulas CH₂CH [ SiMe₂C₆H₄‐SiMe₂CHCH ] ( 16, 17, 18 ) and CH₂CH [ (R)CHCHC₆H₄CHCH ] (where R= Me₂Si‐p C₆H₄‐ SiMe₂ ,  Me₂Si‐m C₆H₄SiMe₂ and  Me₂SiC₆H₄C₆H₄SiMe₂ ) ( 19, 20, 21 ) have been effectively synthesized via silylative coupling (SC) homopolycondensation of bis(vinyldimethylsilyl)arenes ( 10, 12, 14 ) and cross‐polycondensation of 4‐(vinyldimethylsilyl)styrene ( 11 ) as well as cross‐copolycondensation of bis(vinyldimethylsilyl)arenes ( 10, 12 and 14 ) with 1,4‐divinylbenzene ( 9 ) catalyzed by [RuH(Cl)(CO)(PCy₃)₂] ( 7 ). Such highly stereoregular products cannot be synthesized via ADMET polycondensation or ring opening metathesis ROM or polyaddition of hydridosilanes to acetylenes.     

Ferrocene clicked polypyrrole derivatives: effect of spacer group on electrochemical properties and post-polymerization functionalization

In this study, novel ferrocene-functionalized N-alkyl substituted pyrrole derivatives, namely 4-ferrocenyl-1-[3-(pyrrol-1-yl)propyl]-1H-1,2,3-triazole (Py3Fc), 4-ferrocenyl-1-[4-(pyrrol-1-yl)butyl]-1H-1,2,3-triazole (Py4Fc), and 4-ferrocenyl-1-[6-(pyrrol-1-yl)hexyl]-1H-1,2,3-triazole (Py6Fc), were synthesized via click reaction and the monomers were characterized by ¹H NMR, ¹³C NMR, FTIR, and HRMS techniques. Redox properties of the monomers were investigated by cyclic voltammetry (CV) studies. Contrary to general literature, both Py4Fc and Py6Fc were electrochemically polymerized without loss in redox activity of ferrocene group. Moreover, click chemistry was utilized in post-polymerization functionalization. For this purpose, three azide-containing polypyrroles, P(Py3N₃), P(Py4N₃), and P(Py6N₃) were electrochemically synthesized and subjected to click reaction in the presence of ethynylferrocene. CV studies of the post-polymerization functionalized polymers revealed quasi-reversible waves, while only P(Py6-post-Fc) showed the characteristic redox behavior of both polypyrrole and ferrocene. Thus, in this study preparation of a conducting homopolymers of pyrrole having covalently bonded ferrocene units was demonstrated and effect of spacer group is investigated.     

Selective Complexation and Membrane Transport of Guanidinium Salts by Calix[6]arene Amides

The p-tert-butylcalix[6]arene hexamide 2 and syn-1,3,5–trimethoxy-2,4,6-triamide 4 were synthesized by reaction of α-chloro-N,N-diethylacetamide and the corresponding calix[6]arenes 1 and 3 , respectively. ¹H NMR spectroscopy shows that 2 is a mixture of different conformations whereas 4 is fixed in a cone conformation. Extraction experiments, (S-L) and (H₂O–CDCl₃) with picrate salts, indicate that 2 complexes both alkali metal (1:2 complex) and guanidinium salts (1:1 complex) but 4 complexes only guanidinium (1:1 complex). Incorporated in supported liquid membranes (Accurel^® / o-nitrophenyl n-octyl ether) the calixarenes 2 and 4 transport guanidinium salts. The hexamide 2 is a more efficient carrier of guanidinium but the syn-1,3,5-trimethoxy-2,4,6-triamide 4 is much more selective. Both 2 and 4 are sufficiently lipophilic to give membranes that are stable over longer periods (weeks).