2,6-Bis(benzoxazoyl)pyridine (bzpybox) as a new dialkylammonium cation receptor

2,6-Bis(2-benzoxazoyl)pyridine (bzpybox) ligand is reported as a new artificial receptor for secondary dialkylammonium.     

Properties of nylon 6 anionically obtained with NaAl(Lac)4 catalyst and polymerization of ϵ-caprolactam with NaAl(Lac)3(OEt) catalyst

The m-cresol-insoluble polymer of ?-caprolactam obtained with NaAl(Lac)₄ catalyst is converted to a soluble polymer on treatment with dilute (0.1 wt-%) aqueous hydrochloric acid without any accompanying degradation of polymer chain. Aluminum contained in the polymer was not removed completely by extensive extraction with methanol, regardless of the solubilities of the polymers. This fact suggests the existence of two forms of aluminum in the polymer: one contributes to insolubility of the polymer and the other does not. The polymerization behavior in the case of NaAl(Lac)₃(OEt) was somewhat different from that of NaAl(Lac)₄ and of NaAl(Lac)₃(NHBu). These results are considered to reflect a difference in the stability of the Al-O, Al-(Lac), and Al-N bonds in the catalyst.     

Reaction of ethyl 3-ethoxymethylene-2,4-dioxovalerate and ethyl ethoxymethyleneoxaloacetate with 3-aminopyrazole analogs. Synthesis and chemistry of 3,6,7-trisubstituted pyrazolo[1,5-a]pyrimidine derivatives

The chemical reactivity of a series of 3-substituted-6-acetyl-7-carbethoxypyrazolo[l,5-a]pyrimidines ( 6a,b,c ) and 3-substituted-6,7-dicarbethoxypyrazolo[1,5-a]pyrimidines ( 7a,b,c ), prepared by the condensations of the 3-aminopyrazole analogs ( 3a,b,c ) with ethyl 3-ethoxymethylene-2,4-dioxovalerate ( 1 ) or ethyl 3-ethoxymethyleneoxaloacetate ( 2 ), was investigated. Catalytic hydrogenation of 6 or 7 afforded 4,7-dihydro derivatives ( 8 or 9 ). Treatment of 6a,b with acetic acid and water underwent ring transformation into 6H-pyrazolo[1,5-a][1,3]diazepin-6-ones ( 17a,b ). By treatment with phenylhydrazine compounds of type 6 underwent cyclization to yield 2H-dipyrazolo[1,5-a:4′,3′-e]pyrimidines ( 18a,b,c ). Compounds 6 or 7 were treated with an excess of diazomethane at room temperature to give 5-methyl-6H-cyclopropa[5a,6a]pyrazolo-[1,5-a]pyrimidines ( 24 and 25 ) in excellent yields. However, when this reaction was carried out under ice cooling, only compounds of type 23 were isolated. Reaction of 6a with ethyl diazoacetate is also described.     

Synthesis and characterization of soluble aromatic polyurea-amides from new N,N′--dimethyl-N,N′-bis(aminophenyl)ureas and aromatic dicarboxylic acid chlorides

Aromatic polyurea-amides having inherent viscosities of 0.36–0.67 dL/g were synthesized by the low temperature solution polycondensation of new N,N′-dimethyl-N,N′-bis(aminophenyl)ureas with various aromatic dicarboxylic acid chlorides. All the polymers were amorphous, and most of them were soluble in a variety of organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide (DMAc), m-cresol, and pyridine. Some of the polymers could be cast from the DMAc solutions into transparent and flexible films having good tensile properties. The glass transition temperatures of the polyurea-amides obtained from the bis(4-aminophenyl)-substituted ureas were 244–272°C. The temperatures of 10% weight loss under nitrogen of the polymers were in the range of 430 and 480°C. © 1995 John Wiley & Sons, Inc.     

Potent and specific sialyltransferase inhibitors: imino-linked 5a'-carbadisaccharides

Methyl 5a'-carba-beta-lactoside, imino-linked, has been shown to possess potent and specific inhibitory activity (IC50 = 185 microM) toward rat recombinant alpha2,3-sialyltransferase.     

Monomer-catalyst complexes in the stereospecific polymerization of aliphatic aldehyde. The structure and chemical behavior of the aldehyde complex of [R2AlOCR′NPh]2

The reaction between some aliphatic aldehydes (acetaldehyde, propionaldehyde and butyraldehyde) and the typical stereospecific polymerization catalyst R₂AlOCR′NPh has been studied in an attempt to elucidate the initiation mechanism of the polymerization reaction. The monomer-catalyst (1/1) complexes obtained from these aldehydes and R₂AlOCR′NPh possess excellent catalytic activity towards the stereospecific polymerization. The structure of the complex in solution has been determined by NMR and IR spectra and compared with the structure determined by X-ray structure analysis. The presence of pentacoordinate aluminum in the complex has been demonstrated, for the first time, by X-ray studies.The structure of the aromatic monoaldehyde complex has also been studied and shown to be identical with that of the aliphatic aldehyde complex mentioned above. The chemical behavior of these aldehyde complexes towards Lewis bases and Lewis acids has also been studied. The aldehyde moiety of the R₂AlOCR′NPh - MeCHO complex is liberated by the action of a strong Lewis base such as trimethylamine oxide and hexamethylphosphoramide, and is easily exchanged for another kind of aldehyde. The trimethylaluminum complex, Me₂AlOCPhNPh · MeCHO · AlMe₃, which only leads to the formation of amorphous polyacetaldehyde in contrast to Me₂AlOCPhNPh · MeCHO, has been isolated and its structure determined by IR, NMR and X-ray studies in order to establish the relationship between its structure and its chemical behavior.     

High-temperature polymerization of ϵ-caprolactam by using as catalyst the Li,Na, or K salts derived from MAlEt4 or MOAlEt2·AlEt3 and monomer

High-temperature polymerization of ?-caprolactam by using the salts derived from MAlEt₄ (where M is Li, Na, and K) and monomer as catalyst was carried out. Polymerization occurs at 140–170°C, a temperature at which alkali metal caprolactamate has almost no catalytic activity for initiation. m-Cresol-insoluble polymer was obtained at temperatures lower than 231°C. Formation of a m-cresol-insoluble polymer depends on the polymerization temperature and time, and was observed under conditions where Al(Lac)₃ has no catalytic activity. All the polymers obtained by NaAl(Lac)_4–n(NHBu)_n (n = 1 or 2) at 202°C were soluble in m-cresol. These trends observed in the case of MAl(Lac)₄ are considered to be due to initiation by Al(Lac)₃, which is a component of the catalyst used.     

Hydrogen‐bond‐assisted syndiotactic‐specific radical polymerizations of N‐alkylacrylamides: The effect of the N‐substituents on the stereospecificities and unusual large hysteresis in the phase‐transition behavior of aqueous solution of syndiotactic poly(N‐n‐propylacrylamide)

The radical polymerizations of N‐alkylacrylamides, such as N‐methyl‐(NMAAm), N‐n‐propyl‐(NNPAAm), N‐benzyl‐(NBnAAm), and N‐(1‐phenylethyl)acrylamides (NPhEAAm), at low temperatures were investigated in the absence or presence of hexamethylphosphoramide (HMPA) and 3‐methyl‐3‐pentanol (3Me3PenOH), which induced the syndiotactic specificities in the radical polymerization of N‐isopropylacrylamide (NIPAAm). In the absence of the syndiotactic‐specificity inducers, the syndiotacticities of the obtained polymers gradually increased as the bulkiness of the N‐substituents increased. Both HMPA and 3Me3PenOH induced the syndiotactic specificities in the NNPAAm polymerizations as well as in the NIPAAm polymerizations. The addition of 3Me3PenOH into the polymerizations of NMAAm significantly induced the syndiotactic specificities, whereas the tacticities of the obtained polymers were hardly affected by adding HMPA. In the polymerizations of bulkier monomers, such as NBnAAm and NPhEAAm, HMPA worked as the syndiotactic specificity inducer at higher temperatures, whereas 3Me3PenOH hardly influenced the stereospecificity, regardless of the temperatures. The phase‐transition behaviors of the aqueous solutions of poly(NNPAAm)s were also investigated. It appeared that the poly (NNPAAm) with racemo dyad content of 70% exhibited unusual large hysteresis between the heating and cooling processes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4575–4583, 2008