Substitution and elimination reactions of poly(epichlorohydrin) and poly(2-chloroethyl vinyl ether) using phase transfer catalysis

The reactions of poly(epichlorohydrin) (PECH) and poly(2-chloroethyl vinyl ether) (PCEVE) with various reagents were investigated using phase transfer catalyst (PTC) such as tetra-n-butylammonium bromide (TBAB), 18-crown-6 (CR6), and dicyclohexyl-18-crown-6 (DCHC) is a solid—liquid two-phase system. Although the reactions of these polymers hardly occurred without PTC in nonpolar solvents such as toluene and diglyme under mild conditions, the addition of PTC caused the reactions to proceed smoothly under the same conditions. In addition, the reactions of PECH and PCEVE with a strong base such as potassium hydroxide proceeded selectively through β-elimination reaction to produce the polymers with pendant vinyl groups. These results suggested this method is useful for the syntheses of functional polymers. On the other hand, it turned out that quaternary ammonium salts such as TBAB have higher catalytic activity than crown ethers such as CRG and DCHE in these reactions. Furthermore, the catalytic activity of quaternary ammonium salts was strongly influenced by their chain length and the structure of the polymers.     

Hydrophilic polymer-immobilized lipoamides-iron(II) system as a new reducing catalyst for the reduction of O-benzylhydroxylamine by sodium borohydride

Based on a redox function of 1,2-dithiolane ? 1,3-dithiol, lipoamide immobilized on hydrophilic polymers such as polyacrylamide, polyethyleneimine, and chitosan was found to work as polymeric reducing catalysts for the reduction of O-benzylhydroxylamine to benzyl alcohol and ammonia with sodium borohydride in the presence of ferrous ion. These polymers were easily separable and maintained high reactivities even after repeated uses.     

Preparation and properties of monoorganoantimony tetrachloride adducts

Several adducts of monoorganoantimony tetrachlorides, RSbCl₄L (R = CH₃, C₆H₅, p-CH₃C₆H₄; L = HMPT, PyO, 4-CH₃PyO, DMSO), were prepared. In the solid state all of these adducts are stable at room temperature. They are monomeric in solution, and the existence of hexacoordinate antimony is indicated. CH₃SbCl₄L (L = PyO, 4-CH₃PyO) exists in two isomeric forms in solution and decomposes above 70° into CH₃Cl and SbCl₃L. CH₃SbCl₄(HMPT) decomposes in a similar manner even at room temperature.     

Effects of digital processing on repeatability assessment of a multiple reaction monitoring liquid chromatography–tandem mass spectrometry system by ISO 11843-7

ISO 11843 part 7 (ISO 11843-7) can provide a standard deviation (SD) of area measurements of a target peak through the stochastic behaviors of instrumental noises. The purpose of this study is to demonstrate that ISO 11843-7 can be applied to assess repeatability in an isocratic liquid chromatography–tandem mass spectrometry (LC–MS/MS) system without repetitive measurements. The relative standard deviation (RSD) of the peak area of ergosterol picolinyl ester, which was used as an example, on a multiple reaction monitoring (MRM) chromatogram was determined by ISO 11843-7. The RSD by ISO 11843-7 (N = 1) was within a 95% confidence band of the RSD by repetitive measurements (N = 6). Moreover, the effects of digital smoothing, such as moving average, were also examined on the repeatability assessment in LC–MS/MS by ISO 11843-7. From the results of the comparisons of the RSDs obtained by ISO 11843-7 and the repetitive measurements, it was shown that suitable RSDs of the peak area were obtained from the smoothed MRM chromatograms by the moving average for narrow data point windows (e.g., one-sixth of the peak width). In conclusion, the utility of repeatability assessment based on ISO 11843-7 has been expanded for the validation of an LC–MS/MS system.     

Halichonadins A-D, new sesquiterpenoids from a sponge Halichondria sp.

A new dimeric sesquiterpenoid with two eudesmane skeletons through a urea linkage, halichonadin A (1), as well as three new eudesmane sesquiterpenoids having a carbamate, an isonitrile, or an amino functionality, halichonadins B (2), C (3), and D (4), respectively, have been isolated from a marine sponge Halichondria sp., and the gross structures and relative stereochemistry of 1-4 were elucidated on the basis of spectral data and chemical means.     

About gonyautoxins-I, -II, -III,and -IV

The identity of recently reported neurotoxins from $\text{Gonyaulax excavata}$ and Bay of Fundy scallops with previously described gonyautoxins is suggested.     

S,N-heterocycles 2. A convenient,one-pot synthesis of 2-alkylamino-4H-1,3,4-benzothiadiazines

2-Alkylamino-4H-1,3,4-benzothiadiazines 3 are prepared in a one-pot synthesis from 1-phenyl-3-thiosemi-carbazides 1 and bromine through an oxidative cyclization.     

Synthesis and Structure of YbCuGe and YbIrGe

The equiatomic ytterbium–transition metal–germanides YbCuGe and YbIrGe were synthesized in single crystalline form from CuGe and IrGe master alloys and ytterbium via the Bridgman technique and they were characterized through their X-ray powder patterns. The structures were refined from X-ray single crystal diffractometer data: NdPtSb type, P6₃mc, a=421.36(8), c=703.9(1) pm, wR2=0.0234, 210 F² values, 11 variable parameters, BASF=0.35(9) for YbCuGe and TiNiSi type, Pnma, a=671.09(6), b=421.55(5), c=757.16(7) pm, wR2=0.0782, 519 F² values, 20 variable parameters for YbIrGe. The copper (iridium) and germanium atoms build up [CuGe] and [IrGe] networks. In YbCuGe the two-dimensional [CuGe] network consists of puckered layers of Cu₃Ge₃ hexagons (247pm Cu–Ge) that are charge balanced and separated by the ytterbium atoms. In contrast, the ordered Ir₃Ge₃ hexagons show a strong orthorhombic distortion and the [IrGe] network is three-dimensional with a distorted tetrahedral germanium coordination around iridium with almost equal Ir–Ge distances (252–259pm). The ytterbium atoms fill cages within this network. The cell volumes of YbCuGe and YbIrGe are indicative for purely trivalent ytterbium.     

Facile synthesis of p-chloromethylated styrene by elimination reaction of p-(2-bromoethyl)benzylchloride using potassium hydroxide as a base under phase transfer catalysis

Phase transfer catalyzed elimination reactions of $\text{p}$-(2-bromoethyl)-benzylchloride with potassium hydroxide gave $\text{p}$-chloromethylated styrene in high yield.