Synthesis of 2‐substituted‐2,3‐dihydro‐5‐benzoyl‐1H‐1,3,2‐benzodiazaphosphole 2‐oxides/sulfides

Syntheses of 2‐aryloxy/2‐chloro ethoxy‐2,3‐dihydro‐5‐benzoyl‐1H‐1,3,2‐benzodiaza‐phosphole 2‐oxides 3a–h were accomplished by reactions of equimolar quantities of 3,4‐diaminobenzophenone ( 1 ) with various aryl/chloroethoxy phosphorodichloridates 2a–g and 2h in the presence of triethylamine at 50–60°C. Compounds 3i–k were prepared by reacting 3,4‐diaminobenzophenone ( 1 ) with aryl thiophosphorodichloridates 2i–k under similar conditions. They were characterized by IR, ¹H, ¹³C, and ³¹P NMR spectral data. Some of these products possessed siginificant antimicrobial activity © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:340–345, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10044     

2,4,6‐Tri‐tert‐butylphenyl and 2,4‐di‐tert‐butyl‐6‐methylphenyl groups: Look similar,react differently

The crystal structures of molecules with two phosphaalkene groups have been determined. Differences in the stabilization of the PC π‐bond by the 2,4,6‐tri‐tert‐butylphenyl and 2,4‐di‐tert‐butyl‐6‐methylphenyl groups were observed. It has been found that lithium supermesityl(trimethylsilyl)phosphide could be a very efficient base to remove a proton from acetonitrile.© 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:662–666, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10083     

Intramolecular cyclization of ω‐haloalkylsubstituted thiophosphorylacetonitriles: Synthesis and stereochemistry of 3‐cyano‐2‐oxo‐1,2‐thiaphosphacyclanes

Intramolecular S‐alkylation in a series of ω‐haloalkyl‐substituted thiophosphorylacetonitriles 5–7 presents an effective synthetic route to the hitherto unknown 3‐cyano‐2‐oxo‐1,2‐thiaphospholanes 14 and thiaphosphinanes 15 . The compounds were obtained as a mixture of cis‐ and trans‐isomers that were resolved to individual stereoisomers in most cases. For some of them, X‐ray diffraction analysis has been performed. It was shown that ³¹P NMR spectroscopy can be used to assign the stereochemistry of 3‐cyano‐2‐oxo‐1,2‐thiaphosphacyclanes. © 2002 John Wiley & Sons, Inc. Heteroatom Chem 13:1–21, 2002; DOI 10.1002/hc.1101     

“One‐pot” synthesis of (Z)‐2‐aryl‐1‐(2‐cyanoethyl)ethenylphosphonates via hexamethylphosphoramide‐promoted sequential transformation

(Z)‐2‐Aryl‐1‐(2‐cyanoethyl)ethenylphosphonates were synthesized by the hexamethylphosphoramide‐promoted sequential transformation of tetra‐alkyl methanediphosphonates, by the action of potassium tert‐butoxide, and then by acrylonitrile and aldehydes. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:116–119, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10004     

Reactivity of cyanothioformamides and 3‐(4‐bromophenyl)‐5‐imino‐4‐oxazolidinethione toward ortho‐substituted nucleophiles

The substituted benzoazoles 4 and 5a,b were obtained by the reaction of cyanothioformamides 1d and 1b or 1c with o‐substituted aromatic amines 2b and 2c , respectively. Fused pyrimidinones 10, 12 , and 14 were synthesized by the reaction of oxazolidinethione ( 9 ) with 2‐amino aromatic and heteroaromatic carboxylic acids. The structures of the synthesized compounds were established based on elemental analysis and spectral data studies. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:611–616, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10042     

Synthesis of novel N1‐(2‐furanidyl)‐5‐fluorouracil derivatives of α‐hydroxy(thio)phosphonates

Several N¹‐(2‐furanidyl)‐5‐fluorouracil derivatives of α‐hydroxythiophosphonates were synthesized via oxidation by Moffatt's method of N¹‐(2‐furanidyl)‐N³‐(hydroxyalkyl)‐5‐fluorouracil, followed by the addition of diethyl thiophosphite. The phosphonate products were obtained by the oxidation of the corresponding thiophosphonates with m‐chloroperoxybenzoic acid. The crystal structure of compound 6a was determined by X‐ray diffraction. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:211–215, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10021     

Synthesis and characterization of novel poly(vinyl chloride)‐based grafts: Poly(vinyl chloride‐co‐2‐chloropropene) fitted with multiple high‐glass‐transition‐temperature polyolefin branches

The tertiary chlorine (Cl^t) content of vinyl chloride/2‐chloropropene copolymers [P(VC‐co‐2CP)] was determined by NMR spectroscopy. Copolymers containing 6.8–47.0 Cl^t's per P(VC‐co‐2CP) chain were used to initiate the cationic grafting of α‐methylstyrene, norbornadiene, indene, and norbornene with Et₂AlCl under various conditions. Grafting was demonstrated by selective solvent extraction, and the effect of the experimental conditions on the grafting efficiency was examined. Select rheological and thermal characteristics of P(VC‐co‐2CP) grafts, including the glass‐transition temperature, heat deflection temperature, and discoloration upon heating, were studied. P(VC‐co‐2CP) carrying 7–11 poly(α‐methylstyrene) or polynorbornadiene branches per chain raised the glass‐transition temperature to, or above, that of a blend control. P(VC‐co‐2CP)s fitted with polyindene or polynorbornene branches were less effective in raising the mechanical properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3644–3651, 2002     

1H and 13C chemical shifts for acridines: Part XVII. (1,3‐Benzothiazol‐2‐yl)amino‐9(10H)‐acridinone derivatives

The ¹H and ¹³C NMR resonances for 16 acridin‐9(10H)‐ones substituted with amino or (1,3‐benzothiazol‐2‐yl)amino groups were completely and unequivocally assigned by the concerted application of gs‐COSY, gs‐HMQC and gs‐HMBC experiments. Evidence for hydrogen bond and amino–imino tautomerism is presented for 1‐ and 4‐substituted acridin‐9(10H)‐ones. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis,structural analysis,and visualization of poly(2‐ethynyl‐9‐substituted carbazole)s and poly(3‐ethynyl‐9‐substituted carbazole)s containing chiral and achiral minidendritic substituents

The synthesis of 2‐ethynyl‐9‐substituted carbazole and 3‐ethynyl‐9‐substituted carbazole monomers containing first‐generation chiral and achiral dendritic (i.e., minidendritic) substituents, 2‐ethynyl‐9‐[3,4,5‐tris(dodecan‐1‐yloxy)benzyl]carbazole (2ECz), 3‐ethynyl‐9‐[3,4,5‐tris(dodecan‐1‐yloxy)benzyl]carbazole (3ECz), 2‐ethynyl‐9‐{3,4,5‐tris[(S)‐2‐methylbutan‐1‐yloxy]benzyl}carbazole (2ECz*), and 3‐ethynyl‐9‐{3,4,5‐tris[(S)‐2‐methylbutan‐1‐yloxy]benzyl}carbazole (3ECz*), is presented. All monomers were polymerized and copolymerized by stereospecific polymerization to produce cis‐transoidal soluble stereoisomers. A structural analysis of poly(2ECz), poly(2ECz*), poly(3ECz), poly(3ECz*), poly(2ECz*‐co‐2ECz), and poly(3ECz*‐co‐3ECz) by a combination of techniques, including ¹H NMR, ultraviolet–visible, and circular dichroism spectroscopy, thermal optical polarized microscopy, and X‐ray diffraction experiments, demonstrated that these polymers had a helical conformation that produced cylindrical macromolecules exhibiting chiral and achiral nematic phases. Individual chains of these cylindrical macromolecules were visualized by atomic force microscopy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3509–3533, 2002     

Reactions of sterically congested 1,6‐ and 1,7‐bis(diazo)alkanes with elemental sulfur and selenium: Formation of cyclohexene, 1,2‐dithiocane, 1,2‐diselenocane,and 1,2,3‐triselenecane derivatives

The reaction of 3,8‐bis(diazo)‐2,2,4,4,7,7,9,9‐octamethyldecane ( 5 ) with elemental selenium in 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) at 130°C yielded 1,2‐di‐tert‐butyl‐3,3,6,6‐tetramethylcyclohexene ( 1 ) (64%) and trans‐3,8‐di‐tert‐butyl‐4,4,7,7‐tetramethyl‐1,2‐diselenocane ( 8 ) (13%), while that of 5 with elemental sulfur in DBU gave trans‐3, 8‐di‐tert‐butyl‐4,4,7,7‐tetramethyl‐1,2‐dithiocane ( 9 ) (77%). The reaction of 3,9‐bis(diazo)‐2,2,4,4,8,8,10,10‐octamethylundecane ( 6 ) with elemental selenium in DBU at 80°C gave a cyclic triselenide, cis‐4,10‐di‐tert‐butyl‐5,5,9,9‐tetramethyl‐1,2,3‐triselenecane ( 11 ), in 15% yield as the only identifiable product. The structures of 9 and 11 were confirmed by X‐ray crystallography. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:351–356, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10046     

Fragmentation‐related phosphinylations using 2‐aryl‐2‐phosphabicyclo[2.2.2]oct‐ 5‐ene‐ and ‐octa‐5,7‐diene 2‐oxides

A series of new P‐methylphenyl P‐heterocycles are introduced. The para and ortho substituted 2,5‐dihydro‐1H‐phosphole oxides ( 1a and 1b ) were converted to the double‐bond isomers ( A and B ) of 1,2‐dihydrophosphinine oxides ( 3a and 3b ) via the corresponding phosphabicyclo[3.1.0]hexane oxides ( 2a or 2b ). Isomeric mixture ( A and B ) of the dihydrophosphinine oxides ( 3a and 3b ) gave, in turn, the isomers ( A and B ) of phosphabicyclo[2.2.2]oct‐5‐enes ( 4a and 4b ) or a phosphabicyclo[2.2.2]octa‐5,7‐diene ( 5 ) in Diels‐Alder reaction with dienophiles. The bridged P‐heterocycles ( 4 and 5 ) were useful in the photo‐ or thermoinduced fragmentation‐related phosphinylation of hydroxy compounds and amines. The new precursors ( 4a and 4b ) were applied in mechanistic investigations. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:443–451, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10176     

Synthesis and antimicrobial activity of N‐substituted N′‐[6‐methyl‐2‐oxido‐1,3,2‐dioxaphosphinino(5,4‐b)pyridine‐2‐yl]ureas

N‐Substituted N′‐[6‐methyl‐2‐oxido‐1,3,2‐dioxaphosphinino(5,4,‐b)pyridine‐2‐yl]ureas have been accomplished by condensation of equimolar quantities of chlorides of various carbamidophosphoric acids ( 3 ) with 3‐hydroxyl‐6‐methyl‐2‐pyridinemethanol (lutidine diol) ( 4 ) in the presence of triethylamine in dry toluene–tetrahydrofuran (1:1) mixture at 45–50°C. Their structures were established by elemental analyses, IR, ¹H NMR, ¹³C NMR, and ³¹P NMR spectral data. Their antifungal and antibacterial activity is also evaluated. Most of these compounds exhibited moderate antimicrobial activity in the assays. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:509–512, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10181     

Specific interactions and phase behavior of ternary poly(2‐vinylpyridine)/poly(N‐vinyl‐2‐pyrrolidone)/bisphenol A blends

Hydrogen‐bonding interactions between bisphenol A (BPA) and two proton‐accepting polymers, poly(2‐vinylpyridine) (P2VPy) and poly(N‐vinyl‐2‐pyrrolidone) (PVP), were examined by Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The Flory–Huggins interaction‐energy densities of BPA/P2VPy and BPA/PVP blends were determined by the melting point depression method. The interaction parameters for both BPA/P2VPy and BPA/PVP blend systems were negative, demonstrating the miscibility of BPA with P2VPy as well as PVP. The miscibility of ternary BPA/P2VPy/PVP blends was examined by DSC, optical observation, and solid‐state nuclear magnetic resonance spectroscopy. The experimental phase behavior of the ternary blend system agreed with the spinodal phase‐separation boundary calculated using the determined interaction‐energy densities. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1125–1134, 2002     

Enantioselective reduction of dialkyl 4‐(dialkoxyphosphoryl)‐3‐oxobutanoates by baker's yeast

Dialkyl 4‐(dialkoxyphosphoryl)‐3‐oxobutanoates ( 1 ), upon yeast‐mediated bioreduction, afforded chiral dialkyl 4‐(dialkoxyphosphoryl)‐3‐hydroxybutanoates ( 2 ) in moderate to good yields and ee values. Significant improvement was reported for the preparation of dialkyl 4‐(dialkoxyphosphoryl)‐3‐oxobutanoates ( 1 ), the key substrates of this bioreductive conversion. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:153–156, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10011     

Synthesis of phosphorylated 1,3,5‐oxadiazines via N‐acyltrifluoroacetimidoylphosphonates

N‐Benzoyl‐ and N‐methoxycarbonyltrifluoroacetimidoylphosphonates react with dimethylcyanamide in a [4+2]‐cycloaddition to give 4‐phosphorylated 1,3,5‐oxadiazines. The structures of the products were confirmed by NMR (¹H, ¹³C, ¹⁹F, ³¹P) and IR spectra and by XRD analysis. © 2002 John Wiley & Sons, Inc. Heteroatom Chem 13:22–26, 2002; DOI 10.1002/hc.1102     

NMR studies on 1,2‐dihydro‐2‐(4‐aminophenyl)‐4‐[4‐(4‐aminophenoxy)‐4‐phenyl]‐(2H)phthalazin‐1‐one

An unsymmetrical heterocyclic diamine, 1,2‐dihydro‐2‐(4‐aminophenyl)‐4‐[4‐(4‐aminophenoxy)‐4‐phenyl]‐(2H)phthalazin‐1‐one, was synthesized. Its ¹H and ¹³C NMR spectra were completely assigned by utilizing the two‐dimensional heteronuclear ¹³C–¹H multiple‐bond coherence (HMBC) spectroscopy, and heteronuclear ¹³C–¹H one‐bond correlation spectroscopy, homonuclear shift correlation spectroscopy (H,H‐COSY) and rotating frame Overhauser enhancement spectroscopy (ROESY). The structure of the compound was shown to be the phthalazinone rather than the phthalazine ether from cross peaks and chemical shifts of the protons. Copyright © 2002 John Wiley & Sons, Ltd.     

NMR study on 9‐S and 9‐R oxirane derivatives of ascomycin

Structure elucidation of 9‐S and 9‐R oxirane derivatives of ascomycin, a 23‐membered immunomodulating macrolactam, was performed using NMR spectroscopy. The total ¹H and ¹³C signal assignments required the gradient‐selected versions of COSY (gs‐COSY), heteronuclear multiple quantum‐correlation spectroscopy (gs‐HSQC), heteronuclear multiple‐bond correlation spectroscopy (gs‐HMBC), and nuclear Overhauser methods. The data sets then were used to examine the dependence of ketone–hemiketal and cis–trans amide equilibria on the substitution pattern and the absolute configuration of the chiral oxirane. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis and reactions of indane‐1,3‐dione‐2‐thiocarboxanilides with hydrazonoyl halides and active chloromethylene compounds

A novel synthesis of thiadiazoline derivatives 12 and 14 via treatment of indane‐1,3‐dione‐2‐thiocarboxanilides ( 5 ) with hydrazonoyl halides 1 and 2 is reported. Also, active chloromethylene compounds 15 react with 5 to give thiazole derivatives 19 . © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:585–591, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10132     

Catalytic hydrolysis of p‐nitrophenyl picolinate by copper(II) and zinc(II) complexes of N‐(2‐deoxy‐β‐D‐glucopyranosyl‐2‐salicylaldimino)

D‐glucosamine Schiff base N‐(2‐deoxy‐β‐D‐glucopyranosyl‐2‐salicylaldimino) and its Cu(II) and Zn(II) complexes were synthesized and characterized. The hydrolysis of p‐nitrophenyl picolinate (PNPP) catalyzed by ligand and complexes was investigated kinetically by observing the rates of the release of p‐nitrophenol in the aqueous buffers at 25°C and different pHs. The scheme for reaction acting mode involving a ternary complex composed of ligand, metal ion, and substrate was established and the reaction mechanisms were discussed by metal–hydroxyl and Lewis acid mechanisms. The experimental results indicated that the complexes, especially the Cu(II) complex, efficiently catalyzed the hydrolysis of PNPP. The catalytic reactivity of the Zn(II) complex was much smaller than the Cu(II) complex. The rate constant k_N showing the catalytic reactivity of the Cu(II) complex was determined to be 0.299 s^?1 (at pH 8.02) in the buffer. The pK_a of hydroxyl group of the ternary complex was determined to be 7.86 for the Cu(II) complex. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 345–350, 2002     

Synthesis,characterization, and biological studies of tri‐ and diorganotin(IV) complexes with 2′,4′‐difluoro‐4‐hydroxy‐[1,1′]‐biphenyle‐3‐carbolic acid: Crystal structure of [(CH3)3Sn(C13H7O3F2)]

Eight tri‐ and diorganotin(IV) carboxylates with general formulae R₃SnL and R₂SnL₂ (where R = CH₃, n‐C₄H₉, C₆H₅, C₇H₇, and L = 2′,4′‐difluoro‐4‐hydroxy‐[1,1′]‐biphenyl‐3‐carboxylic acid) were synthesized and characterized by UV–vis, IR, conductance, multinuclear (¹H, ¹³C, and ¹¹⁹Sn) NMR spectroscopy, and mass spectrometry. The crystal structure of [(CH₃)₃Sn(C₁₃H₇O₃F₂)] indicates that the tin atom in the asymmetric unit exists in a trigonal bipyramidal geometry having a space group Pbca with an orthorhombic crystal system. These complexes were also screened for their antibacterial and antifungal activities. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:638–649, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10057