Coordination-insertion copolymerization of allyl monomers with ethylene

Coordination-insertion copolymerization of allyl monomers with ethylene was developed by using a palladium/phosphine-sulfonate catalyst. A variety of allyl monomers, including allyl acetate, allyl alcohol, protected allylamines, and allyl halides, were copolymerized with ethylene to form highly linear copolymers that possess in-chain -CH(2)CH(CH(2)FG)- units.     

One-Pot Reduction of Sulfoxides with NaBH4, CoCl2 · 6H2O Catalyst,and Moist Alumina

Sulfoxides are reduced by a combination of sodium borohydride, a catalytic amount of cobalt(II) chloride hexahydrate, and chromatographic neutral alumina preloaded with a small amount of water (moist alumina) in hexane to produce the corresponding sulfides in good to excellent yields under mild conditions. An interesting structural influence of sulfoxides on their reactivity is observed.

Deaminocolchinyl Methyl Ether: Synthesis from 2,3,4,4′-Tetramethoxybiphenyl-2-carbaldehyde. Comparison of antitubulin effects of deaminocolchinyl methyl ether and dehydro analogs

Synthesis of deaminocolchinyl methyl ether 9 was achieved from tetramethoxy-substituted biphenyl-2-carb-aldehyde 12 via tricyclic ketone 20 and 5,6-didehydro congener 11 . Compound 9 was identical in every respect with material prepared from colchicine via 6,7-didehydro congener 10 . Measuring inhibition of tubulin polymerization in vitro showed compounds 4 , 5 , and 9 – 11 of the alloseries of colchicinoids to be particularly potent inhibitors.     

Anion-exchange separation of Te(IV) from Te(VI), Se(IV) and Se(VI) on deae-cellulose in mixed hydrochloric-acetic acid media

Te(IV) can be separated from Te(VI), Se(IV) and Se(VI) by adsorption of Te(IV) on a DEAE-cellulose column from a mixed 1M hydrochloric acid-acetic acid solution (1:9, v/v). This allows a selective separation of Te (IV) from the other three species in widely different mole ratios.     

Preparation of poly(phosphate ester)s having bisphenol moieties as mesogenic units in the main chain

Poly(phosphate ester)s, PPE 1a–d , were synthesized from polycondensation of methyl phosphorodichloridate (MPDC) with various bisphenols such as 4,4′-biphenol 1a , 4,4′-dihydroxyphenylether 1b , bis(4-hydroxyphenyl)methane 1c , and 3,3′-dimethyl-4,4′-dihy-droxybiphenyl 1d . PPE 2a–d with hexamethylene spacers were also obtained from poly-condensation of MPDC with 4,4′-bis(6-hydroxyhexyloxy)biphenyl 2a , 4,4′-di(6-hydroxyhexyloxy)phenyl ether 2b , bis[4-(6-hydroxyhexyloxy)phenyl]methane 2c , and 3,3′-dimethyl 4,4′-di(6-hydroxyhexyloxy)biphenyl 2d . The degree of crystallinity of PPE 1a–1d without hexamethylene spacer was 3.3–17.6%, whereas PPE 2a and PPE 2b which exhibit mesomorphic behavior were 20.1 and 18.6%, respectively. PPE 2a and PPE 2b show the mesophase at 139.6–195.5°C and 42.4–66.3°C, respectively. PPE 2c and PPE 2d were obtained as rubbery. From pyrolysis of PPE in air the temperature corresponding to 5% weight loss was found to be 322–408°C and 284–291°C for PPE 1 and PPE 2 , respectively. It was also found that PPE 2a was enzymatically degraded by phospholipase C. © 1994 John Wiley & Sons, Inc.     

ALS (acidic lithium sulphate) decomposition method (part iv) Kjeldahl determination of nitrogen in heterocyclic ring compounds containing nitrogennitrogen bond

Heterocyclic ring compounds containing nitrogennitrogen bonds such as 1H-1,2,4 triazole, 2,4,6 trimethylbenzenesulfonyltriazolide and pyridazine can be completely decomposed in the molten state with mixtures of various ratios of concentrated sulphuric acid and lithium sulphate (molten ALS) flux containing a catalyst such as silver sulphate. The quantitative recovery of nitrogen in the above three compounds with the molten ALS flux decomposition system can be obtained by the Kjeldahl method.     

Cellulose acetate/poly(methyl methacrylate) interpenetrating networks: synthesis and estimation of thermal and mechanical properties

IPN-type composites consisting of cellulose acetate (CA) and poly(methyl methacrylate; PMMA) were successfully synthesized in film form. In this synthesis, a mercapto group (SH)-containing CA, CA-MA, was prepared in advance by esterification of CA with mercaptoacetic acid, and then intercomponent cross-linking between CA-MA and PMMA was attained by thiol–ene polymerization of methyl methacrylate (MMA) onto the CA-MA substrate. For comparison, polymer synthesis was also attempted to produce a semi-IPN type of composites comprising CA and cross-linked PMMA, via copolymerization of MMA and ethylene glycol dimethacrylate as cross-linker in a homogeneous system containing CA solute. Thermal and mechanical properties of thus obtained polymer composites were investigated by differential scanning calorimetry, dynamic mechanical analysis, and a tensile test, in correlation with the mixing state of the essentially immiscible cellulosic and methacrylate polymer components. It was shown that the specific IPN technique using thiol–ene reactions usually resulted in a much better compatibility-enhanced polymer composite, which exhibited a higher tensile strength and even an outstanding ductility without parallel in any film sample of CA, PMMA, and their physical blends.     

Regioselective Aromatic Monobromination of Alkyl Phenyl Ethers with NaClO2, NaBr,Mn(acac)3, and Montmorillonite K10 in Dichloromethane

Regioselective and high-yielding nuclear monobromination of aromatic ethers can be accomplished with a combination of NaClO₂, NaBr, and Mn(acac)₃ catalyst in dichloromethane under mild and neutral conditions with the aid of Montmorillonite K10.