Heteropolyacid-catalyzed synthesis of chloromethyl methyl ether

An efficient (in terms of experiment and time) synthetic procedure for chloromethyl methyl ether (MOM-Cl) is described using heteropolyacids as catalysts.     

Thermal analysis of polystyrenes crosslinked by p-di(chloromethyl)benzene

Series of progressively crosslinked polystyrene have been prepared by the reaction off linear polystyrene with p-di(chloromethyl)benzene in dichloroethylene solution with stannic chloride as catalyst. By using a DTA technique it has been shown that the glass transition temperature T_g increases with crosslinking very much faster than is accounted for purely by increase in molecular weight. This type of crosslink is only about half as effective in increasing T_g as are crosslinks introduced by copolymerization of styrene with divinylbenzene. Thermal analysis by use of the thermal volatilization analysis (TVA) technique shows that stability, as measured by the evolution of volatile products, decreases as crosslinking progresses, and thermal gravimetric analysis (TGA) confirms this.     

Thermal oxidation of blends of poly(vinyl methyl ether) and modified polystyrenes

Thermal oxidation of blends of poly(vinyl methyl ether) and styrene copolymers containing hydroxyl groups as hydrogen-bond donors was studied. The hydrogen-bonding interaction provide for improved miscibility between the component polymers and more extensive crosspropagation/cross-termination reactions. In addition to their contribution to improved miscibility, phenol groups in the copolymers exhibited apparent antioxidant and prooxidant effects.     

Tracer diffusion of star-branched polystyrenes in poly(vinyl methyl ether) gels

The tracer diffusion of 3-, 4-, and 12-arm polystyrene (PS) stars in poly(vinyl methyl ether) (PVME) gels has been measured by dynamic light scattering (DLS). The intensity correlation functions were analyzed by two methods. One was that employed previously in a DLS study of linear PS diffusion in PVME gels [N. A. Rotstein and T. P. Lodge, Macromolecules, Vol. 24. p. 1316 (1992)], and the other was based on consideration of possible nonergodicity effects [P. N. Pusey and W. van Megen, Physica A, Vol. 157, p. 705 (1990)]. Both methods gave equivalent results, suggesting that nonergodicity plays a small role in this system. This conclusion is not unreasonable, given that the PVME gels are almost isorefractive with the solvent (toluene), and that the signal is dominated by scattering from the PS chains. The resulting star diffusivities are consistently less than or equal to those for linear probes of comparable size, with the difference increasing with molecular weight. The diffusivities are also less than or equal to those obtained for the same stars in PVME solutions. A weak dependence on the number of arms is also observed. Finally, the mobility of a given star in a gel is much more sensitive to variations in the average molecular weight between cross-links than is the mobility of a linear chain. All of these features in the data are broadly consistent with the reptation hypothesis. © 1993 John Wiley & Sons, Inc.     

Simple, rapid procedure for the synthesis of chloromethyl methyl ether and other chloro alkyl ethers

[Reaction: see text]. Zinc(II) salts catalyze the reaction between acetals and acid halides to provide haloalkyl ethers in near-quantitative yield. Reactions from millimole to mole scale are typically complete in 1-4 h with 0.01 mol % catalyst. The solutions of haloalkyl ethers thus obtained can be utilized directly in reactions in which the presence of the ester byproduct does not interfere. Excess haloalkyl ether is destroyed on workup, thereby minimizing exposure to this class of carcinogenic compounds.     

Condensation of chloromethyl propargyl ether with nitriles

Russian Journal of Organic Chemistry - Reactions of aromatic and aliphatic nitriles with chloromethyl propargyl ether in the presence of activated zinc followed by treatment with water in the...     

Friedel–Crafts polymerization of fluorene with methylene chloride,methoxyacetyl chloride,and chloromethyl methyl ether

The polymerization of fluorene with various chloromethylating reagents (methylene chloride, methoxyacetyl chloride, and chloromethyl methyl ether) in the presence of aluminum chloride was studied. The products that were obtained were insoluble, infusible, colored powders which contain a low concentration of aromatic radicals. Each of the polymers is composed predominantly of fluorene nuclei bridged at the 2 and 7 positions by methylene groups. In addition, the materials possess varying amounts of crosslinked and ring-fused moieties. Based on physical and spectral properties and reaction stoichiometry, the fluorene/methylene chloride polymer is the most highly crosslinked of the three. The fluorene/methoxyacetyl chloride and fluorene/chloromethyl methyl ether polymers are similar to each other in most respects.     

Reactions of the carbanion of chloromethyl methyl sulfone with aldehydes and ketones

Addition of the carbanion of chloromethyl methyl sulfone to aldehydes and ketones proceeds faster than its degradation via the Ramberg-Baecklund reaction. Chlorohydrins and oxiranes produced from aldehydes treated with an excess of base undergo the Ramberg-Baecklund reaction giving allylic alcohols, whereas the reaction of ketones gives the oxiranes.     

Determination of low level methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl ether in human urine by HS-SPME gas chromatography/mass spectrometry

Methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME) are oxygenated compounds added to gasoline to enhance octane rating and to improve combustion. They may be found as pollutants of living and working environments. In this work a robotized method for the quantification of low level MTBE, ETBE and TAME in human urine was developed and validated. The analytes were sampled in the headspace of urine by SPME in the presence of MTBE-d12 as internal standard. Different fibers were compared for their linearity and extraction efficiency: carboxen/polydimethylsiloxane, polydimethylsiloxane/divinylbenzene, and polydimethylsiloxane. The first, although highly efficient, was discarded due to deviation of linearity for competitive displacement, and the polydimethylsiloxane/divinylbenzene fiber was chosen instead. The analysis was performed by GC/MS operating in the electron impact mode. The method is very specific, with range of linearity 30-4600 ng L⁻¹, within- and between-run precision, as coefficient of variation, <22 and <16%, accuracy within 20% the theoretical level, and limit of detection of 6 ng L⁻¹ for all the analytes. The influence of the matrix on the quantification of these ethers was evaluated analysing the specimens of seven traffic policemen exposed to autovehicular emissions: using the calibration curve and the method of standard additions comparable levels of MTBE (68-528 ng L⁻¹), ETBE (<6 ng L⁻¹), and TAME (<6 ng L⁻¹) were obtained.     

Photoinitiated polymerization of methyl methacrylate with benzoin methyl ether. III. Independent photogeneration of the ether radical

Evidence is presented for initiation of MMA polymerization by the α-methoxybenzyl (ether) radical, photogenerated by H abstraction from benzyl methyl ether, utilizing benzophenone as the H-ab-stracting agent. The results support previous reports on the initiating ability of ether radical, photogenerated from ¹⁴C-labeled benzoin methyl ethers. Independent generation of one or both of the radicals derived from unsymmetrical initiators is more broadly applicable. The potential utility of this technique for providing insights into the photoefficiencies of commercially important photoinitiators, which produce initiator radicals by intramolecular bond cleavage, is discussed.     

甲基葡萄糖苷硬脂酸酯及其聚氧丙烯醚的合成

以α-甲基葡萄糖苷和硬脂酸甲酯为原料,在碱性催化剂K2CO3和相转移催化剂四丁基氯化铵(TBAC)共同作用下,无溶剂法合成了甲基葡萄糖苷硬脂酸酯(SS),再与环氧丙烷反应,合成了甲基葡萄糖苷硬脂酸酯聚氧丙烯醚(SSP),并对产品进行了IR表征.探讨了相转移催化酯交换反应机理.研究了原料配比、催化剂种类及用量、反应温度、反应时间等因素对SS收率的影响,得到了合成SS的适宜工艺条件:n(甲基葡萄糖苷)∶ n(硬脂酸甲酯)=0.71∶ 1,w(K2CO3)∶ w(硬脂酸酸甲酯)=0.04∶ 1,w(TBAC)∶ w(硬脂酸甲酯)=0.05∶ 1,反应温度145℃,时间4.5h,压力6kPa.上述条件下,SS收率可达92%,产品质量较好.     

Reactions of chloromethyl heptyl ether with selenium and tellurium in the system hydrazine hydrate-potassium hydroxide

Chloromethyl heptyl ether reacts with selenium in the system hydrazine hydrate-potassium hydroxide with formation of a mixture of bis(heptyloxymethyl)selane (32%) and bis(heptyloxymethyl)diselane (64%). Reductive cleavage of the latter with hydrazine hydrate-KOH and subsequent alkylation with methyl iodide gave methyl(heptyloxymethyl)selane in 94% yield. Analogous reaction of tellurium with hydrazine hydrate-KOH leads to the formation of extremely unstable bis(heptyloxymethyl)ditellane and bis(heptyloxymethyl) tellane at a ratio of 1: 4.     

Di-isotacticity of poly(methyl propenyl ether) and double-bond opening of methyl propenyl ether in cationic polymerization

The di-isotacticity of poly(methylpropenyl ether) obtained by the cationic polymerization has been studied by NMR spectra. The NMR spectra of β-methyl protons of the polymer are decoupled from the β-methine proton spectra to determine the di-isotactic fraction in a polymer. The signals of β-methyl protons at 8.78 and 8.89 τ are estimated as spectra based on threo- and erythro-di-isotactic diads, respectively. With BF₃·O(C₂H₅)₂ as a catalyst, the trans monomer yields a crystalline polymer and its structure is threo-di-isotactic. Otherwise, cis monomer produces an amorphous polymer, and it is a mixture of threo- and erythro-di-isotactic structure. From these results, it is concluded that the double bond in trans monomer is opened exclusively in the cis type, and in cis monomer cis- and trans-openings take place at almost the same rate.     

Synthesis of (+)-spirolaxine methyl ether

A short and efficient synthesis of (+)-spirolaxine methyl ether, a metabolite of the fungus Sporotrichum laxum with inhibitory activity against Helicobacter pylori, is described. The synthesis has been carried out by a Prins cyclization, to obtain the [6,5]-spiroketal system, and a Wadsworth-Emmons condensation, applied for the installation of the polymethylene chain on the phthalide moiety.