N-butyl Vinyl Ether Research Articles

Grafting onto wool. XVI. Graft copolymerization of vinyl monomers by use of TBHP–FAS as redox initiator

AbstractMethyl acrylate (MA), methyl methacrylate (MMA), and n‐butyl vinyl ether (n‐BVE) have been graft‐copolymerized onto Himachali wool in an aqueous medium by using tertiary butyl hydroperoxide ferrous ammonium sulfate (TBHP‐FAS) redox system at 40°C, 50°C, 60°C, and 70°C for various reaction periods. Percentage of grafting and percent efficiency have been determined as functions of concentration of monomers, molar ratios of [TBHP]/[FAS], time and temperture. Molar ratios of [TBHP]/[FAS] were found to influence grafting of different monomers studied. Chemical evidence indicates that a covalent bond formation occurs between grafted polymeric chain and backbone polymer. The rate of grafting (Rp) and induction period (Ip) of different monomers towards graft copolymerization were determined as function of total initial monomer concentrations. Rp and Ip of n‐BVE are independent of total initial monomer concentrations while Rp and Ip of both MA and MMA were found to depend on the total initial monomer concentrations. MA, MMA, and n‐BVE were found to differ in reactivity towards grafting onto wool in the presence of (TBHP‐FAS) redox system; the following reactivity order was observed: MMA > MA > n‐BVE.

The mechanisms of thermal eliminations. Part 12. Relative rates of pyrolysis of ethyl, isopropyl, t-butyl, and n-butyl vinyl ethers: rate spread as an index of elimination mechanisms

Rate coefficients have been measured between 594.5 and 681.0 K for pyrolysis of ethyl, isopropy, t-butyl, and n-butyl vinyl ethers. The relative rates of elimination at 600 K are : 1.0, 10.0, 178, and 1.52, the Arrhenius data [E/kJ mol–1, log (A/s–1)] being: ethyl, 185.92, 11.826; isopropyl, 182.51, 12.527; t-butyl, 164.05, 12.169; n-butyl, 177.64, 11.284. These results show that the literature data for t-butyl vinyl ether elimination are considerably in error, confirming the prediction based on statistical mechanics. The relative primary, secondary, and tertiary elimination rates are consistent with those obtained from a range of thermal eliminations, whereas the relative rates based on the literature data are not. Analysis of the relative primary, secondary, and tertiary elimination rates from this and other reactions permits prediction of rates for secondary and tertiary compounds as yet unmeasured, and also suggests that some literature data may be in error through the incursion of side reactions. A β-ethyl group increases the rate of elimination 2,3-fold per β-hydrogen at 600 K (cf. 1.62 for acetates) and may likewise be due to steric acceleration, though the possibility of electron acceptance by alkyl groups in the gas-phase cannot be excluded. The product distribution in pyrolysis of 1-methylpropylvinyl ether is shown to be accounted for by the nature of the transition state. Vinyl ethers do not pyrolyse 50° below the corresponding esters as recently claimed. Tertiary vinyl ethers are for example less reactive than tertiary esters.

Correlation between catalytic cyclopropanation and ylide generation

A linear correlation for catalytic effectiveness exists between cyclopropanation of n-butyl vinyl ether and ylide generation with allyl methyl sulfide in reactions with ethyl diazoacetate. Twenty-two representative transition metal compounds have been examined, and ruthenium is identified for the first time to exhibit catalytic potential comparable to copper and rhodium catalysts for carbene transformations.

Laser-induced multiphoton dissociation of n-butyl ether

The pulsed CO 2-laser-induced multiphoton dissociation of n-butyl vinyl ether is studied. Comprehensive measurements have been performed for 9.6.μm and 10.6 μm irradiation. The corresponding dissociation product distributions show distinct differences for the two irradiation wavelengths, the most important finding being that acetylene is only produced at 9.6 μm.

Alternating copolymers of dimethylmaleic anhydride

Copolymerization of 2, 3-dimethylmaleic anhydride was accomplished with vinyl ethers, particularly n-butylvinyl ether and isobutyl-vinyl ether and gave exactly alternating copolymers in all proportions of feed comonomer compositions. 2,3-Dimethylmaleic anhydride has not yet been copolymerized with vinyl comonomers with less electron donating properties.

The photo-cycloaddition of enol ethers to benzene

The photo-reactions of benzene with ethyl vinyl ether, n-butyl vinyl ether, 1,1 -dimethoxyethylene, 2,3-dihydropyran, 2,3-dihydrofuran, 2,3-dihydro-1,4-dioxin, and 1,3-dioxole are described. The meta-photo-cycloaddition of ethyl vinyl ether and n-butyl vinyl ether to benzene shows little selectivity, and regio- and stereo-isomers are isolated. ortho-Cycloaddition is observed from all systems but only with 2,3-dihydrofuran as addend are both stereoisomers of the adduct formed, and although the exo-isomer is very photolabile, the endo-product is essentially stable under its conditions of formation. The ortho-cycloaddition of 1,1 -dimethoxyethylene to benzene provides the first step in a convenient synthesis of cyclo-octatrienone. Contrary to previous proposals there is little correlation between the stereochemistry of the ortho-cycloaddition and preferred orientation of the addends in the ground state. The relationship between the relative efficiency of the two addition modes and ionisation potential of the ethylene is discussed.

High-pressure kinetics of electron donor–acceptor complex formation and cycloaddition between tetracyanoethylene and enol ethers

The kinetics of the high-pressure cycloaddition reaction between tetracyanoethylene and enol ethers (n-butyl vinyl ether and ethyl 2-methylpropenyl ether) in chloroform have been studied, by following spectrophotometrically the disappearance of the electron donor–acceptor complex (e.d.a. complex) at 25 °C and up to 1 500 bar. It is concluded that the e.d.a. complex is on the pathway to the zwitterionic intermediate and the final cycloaddition product. The reaction volume ΔV1 of e.d.a. complex formation is –11.0 ± 1.4 and –5.8 ± 1.0 cm3 mol–1 for n-butyl vinyl ether and ethyl 2-methylpropenyl ether, respectively. The volume of activation ΔV2‡ of cycloaddition step from e.d.a. complex to the adduct is –30.8 ± 1.5 and –41.8 ± 1.5 cm3 mol–1 for n-butyl vinyl ether and ethyl 2-methylpropenyl ether, respectively. The variation of ΔV1 and ΔV2‡ is discussed from the viewpoint of the ionization potential and the electron density at the β-carbon atom of the enol ether.

Titrimetric studies of p-aminobenzoicacid-formaldehyde- p-bromophenol copolymers in non-aqueous media

latter instance, the slope change also occurs at 1 M vinyl ether concentration. Such a feature implies that above this threshold [IBVE] monomer transfer assumes dominance over other chain breaking reactions. Monomer specificity n-Butyl vinyl ether and N-vinyl carbazole have also been observed to undergo facile polymerization in presence of C6HsCOC1 at ambient temperatures. For the polymerization of Nvinyl carbazole by C6H5COCI, as in the case with POC13, SOC12 and CrO2C12 no colouration was developed in the polymerization system or in the product polymer indicating the absence of charge transfer interactions is.

Structures and formation of \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 4}} {\rm H}_{{\rm 8}} } \right]_{}^{_.^ + } $\end{document} ions

AbstractSeveral \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 4}} {\rm H}_{{\rm\ 8}} } \right]_{}^{_.^ + } $\end{document} ion isomers yield characteristic and distinguishable collisional activation spectra: \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm 1-butene} } \right]_{}^{_.^ + } $\end{document} and/or \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm 2-butene} } \right]_{}^{_.^ + } $\end{document} (a‐b), \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm isobutene} } \right]_{}^{_.^ + } $\end{document} (c) and [cyclobutane]+ (e), while the collisional activation spectrum of \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm methylcyclopropane} } \right]_{}^{_.^ + } $\end{document} (d) could also arise from a combination of a‐b and c. Although ready isomerization may occur for \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 4}} {\rm H}_{{\rm 8}} } \right]_{}^{_.^ + } $\end{document} ions of higher internal energy, such as d or e → a, b, and/or c, the isomeric product ions identified from many precursors are consistent with previously postulated rearrangement mechanisms. 1,4‐Eliminations of HX occur in 1‐alkanols and, in part, 1‐buthanethiol and 1‐bromobutane. The collisional activation data are consistent with a substantial proportion of 1,3‐elimination in 1‐ and 2‐chlorobutane, although 1,2‐elimination may also occur in the latter, and the formation of the methylcycloprpane ion from n‐butyl vinyl ether and from n‐butyl formate. Surprisingly, cyclohexane yields the \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm linear butene} } \right]_{}^{_.^ + } $\end{document} ions a‐b, not \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm cyclobutane} } \right]_{}^{_.^ + } $\end{document}, e.

ChemInform Abstract: VIBRATIONAL SPECTRA AND ROTATIONAL ISOMERISM OF ALKYL VINYL ETHERS

Chemischer InformationsdienstVolume 7, Issue 17 Physical Organic Chemistry ChemInform Abstract: VIBRATIONAL SPECTRA AND ROTATIONAL ISOMERISM OF ALKYL VINYL ETHERS MASAAKI SAKAKIBARA, MASAAKI SAKAKIBARASearch for more papers by this authorFUYUHIKO INAGAKI, FUYUHIKO INAGAKISearch for more papers by this authorISSEI HARADA, ISSEI HARADASearch for more papers by this authorTAKEHIKO SHIMANOUCHI, TAKEHIKO SHIMANOUCHISearch for more papers by this author MASAAKI SAKAKIBARA, MASAAKI SAKAKIBARASearch for more papers by this authorFUYUHIKO INAGAKI, FUYUHIKO INAGAKISearch for more papers by this authorISSEI HARADA, ISSEI HARADASearch for more papers by this authorTAKEHIKO SHIMANOUCHI, TAKEHIKO SHIMANOUCHISearch for more papers by this author First published: April 27, 1976 https://doi.org/10.1002/chin.197617043AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume7, Issue17April 27, 1976 RelatedInformation

Vibrational Spectra and Rotational Isomerism of Alkyl Vinyl Ethers

Abstract The rotational isomerism of methyl vinyl ether, ethyl vinyl ether, and n-butyl vinyl ether has been studied by means of the vibrational spectra and normal frequency calculations. The enthalpy difference between the skew and cis isomers in the liquid state of methyl vinyl ether has been determined to be 1440±160 cal/mol. Series of C–O torsional transitions in the cis well have been observed for methyl vinyl ether and methy-d3 vinyl ether in the region near 230 cm−1 and analyzed. It has been concluded for ethyl vinyl ether that the cis-trans form (CT) is stable in the solid state and that three forms, CT, SG′, and ST, coexist in the liquid and gaseous states. The spectra in the solid state of n-butyl vinyl ether are consistent with the calculated frequencies of the CTTT form.

Model reactions for bacterial bioluminescence

Acid-catalysed addition of hydrogen peroxide to n-butyl vinyl ether gave a separable mixture of the hydroperoxides (1)–(4); peroxides (1)–(3) undergo chemiluminescent reactions in acetonitrile with 1,3,10-trimethylisoalloxazinium perchlorate in the presence of triethylamine, and the flavin analogue catalyses the decomposition of the peroxides.

Polymerization with zeolite catalysts: II. Vinyl ethers over H-mordenite and H-Y

Ethylvinyl, n-butylvinyl and isobutylvinyl ethers all react readily over H-mordenite and H-faujasite (H-Y) near room temperature to produce low molecular weight polymers. Over H-mordenite all follow the kinetic relation, Q t = k(t) 1 2 + γ , where Q t is the mass uptake at constant pressure p and time t. k and γ are coefficients. Over H-Y the kinetics followed the Elovich equation Q t = k ln t + γ. Over both catalysts the rate coefficients were linear functions of pressure, i.e., k = ( ap + b) where a and b are coefficients. As shown previously for n-butylvinyl ether over H-mordenite [Barrer, R. M., and Oei, A. T. T., J. Catal. 30, 460 (1973)], water in small amounts was also a co-catalyst for polymerization of the same vinyl ether over H-Y. The kinetics have been interpreted as indicating that little polymer forms within the channels of mordenite but that within those of faujasite considerable polymer forms and progressively blocks intracrystalline sites. Supporting evidence of this has been obtained by water Sorption in and thermogravimetric analyses of zeolite + polymer composites.

Cyclopropanes from Olefins by the Oxygen-accelerated Zinc-carbenoid Reaction

Abstract Oxygen greatly accelerates the cyclopropanation of olefins by the diethylzinc-chloroiodomethane or -diiodomethane system. Olefins, including cyclohexene, cyclooctene, 1-heptene, 1-octene, 2-heptene, indene, n-butyl vinyl ether, styrene, and methyl oleate, gave the corresponding cyclopropanes in yields of ca. 70–100%. The methylene addition to cis- and trans-2-butene proceeded in a stereospecific manner in the presence of oxygen. Methyl methacrylate gave no appreciable amount of cyclopropanated product, but polymerization proceeded. Styrene inhibited the formation of the zinc-carbenoid reagent from diethylzinc and dihalomethanes under a nitrogen atmosphere. AIBN and UV light initiated the cyclopropanation of styrene with diethylzinc and chloroiodomethane. A free-radical-chain mechanism is proposed for the formation of the zinc-carbenoid reagent from diethylzinc and dihalomethanes.

Cycloaddition reaction between tretracyanoethylene and n-butyl vinyl ether: The solvent dependence of the volume of activation

Cycloaddition reaction between tretracyanoethylene and n-butyl vinyl ether: The solvent dependence of the volume of activation

The Codimerizations of Styrene with Vinyl Compounds Catalyzed by Olefin-palladium(II) Chloride Complexes

Abstract The codimerization of styrene with vinyl compounds catalyzed by di-μ-chloro-dichlorobis(styrene)dipalladium(II), (Pd(C6H5CH=CH2)Cl2)2, was investigated in a homogeneous system under mild conditions. The reaction of styrene and methyl acrylate carried out at 50°C for 6 hr yielded 220% codimers, 169% dimers of methyl acrylate, and 18% dimers of styrene, on the basis of the palladium(II) used. The codimerizations of styrene with vinyl acetate and with methyl vinyl ketone gave 50% codimer and 125% codimers respectively. When nitroethylene and n-butyl vinyl ether were used as the vinyl compound, no codimers were formed. The codimerization of styrene-d3 with ethylene was also carried out. The reaction mechanism involving the five-coordinate hydridopalladiumolefin intermediate was proposed and discussed in the terms of the distribution of deuterium in the codimer of styrene-d3 and ethylene, the functional group effects of vinyl compounds, and solvent effects on the codimerization.

Alternating Copolymers from trans-1, 2-Dibenzoylethylene and trans-1, 2-DiacetylethyIene

Symmetrical α, β-unsaturated carbonyl compounds, trans-1, 2-dibenzoylethylene (DBE) and trans-1, 2-diacetylethylene (DAE) were synthesized and copolymerization with styrene or n-butyl vinyl ether was carried out in the presence of a radical initiator. The apparent over-all rates of the copolymerization of DBE were faster than that of DAE and the addition reaction of DBE with amine was also faster than that of DAE, indicating that the double bond of DBE is more electron-deficient than DAE.The compositions of copolymers from DBE or DAE were constant at the molar ratio of 50 mol%, regardless of the monomer ratios in the feed, although DAE did not copolymerize with n-butyl vinyl ether. No evidence could be found from spectroscopic studies for the formation of a charge-transfer complex between DBE or DAE and donor monomers, and the alternating tendency of the copolymerization could be increased by the strongly favorable polar effect of two carbonyl groups on the double bond of DBE or DAE.Neither DBE nor DAE copolymerized with styrene with an anionic initiator, possibly because they formed anions too stable to initiate copolymerization.

Cationic Polymerization of β-Phenylvinyl Alkyl Ethers

Abstract The cationic polymerization of β-phenylvinyl alkyl ethers (alkyl: methyl, ethyl, n-propyl, and n-butyl) was examined in toluene and in methylene chloride with boron fluoride etherate and with stannic chloride at −78°C. Despite the fact that these monomers have bulky substituents on the α –and β-carbons, they could be homopoly-merized easily even in nonpolar sovent at −78°C. The general features of β-phenylvinyl alkyl ethers in homopolymerization and co-polymerization with n-butyl vinyl ether suggested that β-phenylvinyl alkyl ethers behaved as derivatives of vinyl ethers, not as derivatives of styrenes. The polymerization products were white powders having a high softening point.

The effect of butanol, acetaldehyde and water on the polymerization of vinyl-n-butyl ether in the presence of the sulphuric acid-aluminium sulphate complex

been shown qualitatively by two of us [2] that in the stereospeeific polymerization of vinyl-n-butyl ether (VBE) it is possible to use less thoroughly purified monomer and solvent, which considerably simplifies the technology of production of high molecular weight VBE polymer. In the present work we made a quantitative study of the effect of impurities in VBE on the yield, molecular weight and crystallinity of VBE polymer produced in the presence of the SA-AS complex. Butanol, acetaldehyde and water could be present as impurities in VBE. Butanol is the starting material for the synthesis of VBE by the Favorskii-Shostakovskii method and consequently VBE always contains butanol. Moreover butanol and acetaldehyde are formed by hydrolysis of VBE. In polymerization of VBE in the presence of the SA-AS increase in the butanol content causes decrease in the yield (Fig. 1) and lowering of the molecular weight of the polymer (Fig. 2), the drop in molecular weight being very sharp with increase in the butanol content of the monomer up to 1% by weight while further increase up to 8% causes only decrease in the

The kinetics of ionic polymerisation. Part XIV. Conductivities and visible spectra of iodine–n-butyl vinyl ether mixtures

The system iodine–n-butyl vinyl ether in carbon tetrachloride, diethyl ether, and ethylene dichloride has been studied. The species l4 exists in solutions of iodine in these solvents but is probably not significant in the polymerisation.The absence of any spectral evidence for l3– in polymerising solutions in carbon tetrachloride and diethyl ether suggests that the stationary state concentration of active monomer during polymerisation is only very small. The low conductivities of solutions of iodine and monomer in carbon tetrachloride are in accord with this conclusion.The first and second ionisation potentials of n-butyl vinyl ether are reported. The predicted absorption maxima of the n-butyl vinyl ether–iodine σ- and π-complexes show poor agreement with the experimentally observed absorption bands which have previously been attributed to these complexes. Conductivity measurements show that the termination of polymerisation is accompanied or followed by large increases in the concentration of ions in the solutions. During polymerisation the conductivities of ethylene dichloride solutions are much higher than those of carbon tetrachloride solutions in accord with the higher dielectric constant and the greater rates of polymerisation for the former.