Effect of high pressure on the composition of stereoisomers of the Diels-Alder reaction between furan and maleic anhydride

The kinetic data on the Diels-Alder reaction between furan and maleic anhydride at atmospheric pressure and 20 and 40°C correspond to a scheme of the process which includes transformation of an endo-isomer into an exo-isomer without preliminary decomposition into the starting substances. The reaction is significantly accelerated by an increase in the pressure, and the rate of formation of the exo-isomer is close to the rate of formation of the endo-isomer both at atmospheric and at high pressure. The endo-isomer is obtained with a high yield (up to 45%) at a high pressure, and this permitted determining the rate constant of its decomposition at atmospheric pressure.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2510–2517, November, 1989.     

Effect of pressure on the Diels-Alder reaction between furan and methyl acrylate

A study was carried out on the effect of pressure up to 1400 MPa on the Diels-Alder reaction between furan and methyl acrylate at 20C. At atmospheric pressure, the reaction proceeds with 20% yield after two months, while it proceeds at 1400 MPa with 70% yield after 2.5 h. The observed volumetric activation effect (–V_p ) of this reaction decreases relatively slightly with increasing pressure and its value at 0.1 MPa (20 cm³/mole) is markedly less than the change in volume upon reaction (–V₀=29 cm³/mole). The ratio of the endo and exo isomers formed is 2.6 and is independent of the pressure.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2651–2654, November, 1990.     

The Diels-Alder reaction between substituted 6,6-dimethyl-2-vinylnorpinenes and maleic anhydride

Cycloaddition of substituted 6,6-dimethyl-2-vinylnorpinenes with maleic anhydride occursvia the attack of a dienophile on diene from the less hindered side of the bicyclic fragment. IR, UV, CD, and¹H NMR spectra of adducts have been studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1546–1548, August, 1995.The authors are grateful to I. E. Ismaev for recording several¹H NMR spectra.     

Thermodynamic and kinetic studies on reversible liquid-phase Diels Alder reaction between maleic anhydride and 2-methyl furan

The liquid phase reaction between maleic anhydride and 1-methyl-furan leads to an exothermic cycloaddition. The reaction enthalpy, the rate constant and the equilibrium constant are evaluated with good precision by a method of analysis using thermal data and a dynamic model based on physical properties. The mathematical models that are presented here in a simple way (first-order system) represent the reaction accurately and are useful for studying other reactions and even industrial processes.     

13C and1H NMR spectra and stereoconfiguration of 1,4-adducts of the Diels-Alder reaction of furan with methyl acrylate and maleic anhydride

¹³C and¹H NMR spectra were taken for the 1,4-adducts of furan with methyl acrylate and maleic anhydride. The¹³C chemical shifts are characteristic: these values for C¹, C³, and C⁶ (adducts (I) and (II)) and C¹, C⁴ C², C³, C⁵, and C⁶ (adducts (III) and (IV)) depend on the orientation of the substituent at C² in the case of methyl acrylate and at C² and C³ in the case of maleic anhydride and may be used for the assignment of the adducts to the endo and exo isomers.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1669–1671, July, 1990.     

The high pressure mediated intramolecular Diels-Alder reaction of furan dienes: a synthetic approach towards daphnanes.

Furan $\text{2}$ undergoes intramolecular Diels-Alder reaction when subjected to high (14kbar) pressures to give a mixture of $\text{endo}$ and $\text{exo}$ adducts in which the $\text{exo}$ adduct is formed as the kinetic product, at variance with the expected course of events.     

Copolymerization of furan with maleic anhydride initiated by thioglycolic acid

Copolymerization of furan (F) with maleic anhydride (MAH) initiated by thioglycolic acid (TGA) was studied in various solvents and temperatures in the presence of atmospheric oxygen. Copolymer between F and MAH was readily obtained by using thiol compounds as initiators. The atmospheric oxygen catalyses the copolymerization reaction. The rate of copolymerization is proportional to the concentration [TGA]^0.55 at low concentrations (< 1.0 mol/L), at higher concentrations rates decrease gradually. The copolymerization rate increases with increase in copolymerization temperature and varies with the total monomer concentration as ([F] + [MAH])^1.9. The overall energy of activation as calculated from the Arrhenius plot has been found to be 6.4 Kcal/mol within the temperature range of 25–50°C.     

Diels-Alder reaction of furan with some dienophiles

The reaction of furan and maleic acid was carried out in several solvents. The endo-adduct was isolated and the structure established by its spectral properties and conversion into known compounds. The adducts of furan with fumaric acid, diethyl fumarate and diethyl maleate are reported.     

Effect of pressure on the rate of the Diels-Alder reaction of diethyl azodicarboxylate with 9,10-dimethylanthracene

The enthalpy, entropy, and volume of activation and volume of the Diels-Alder reaction of diethyl azodicarboxylate with 9,10-dimethylanthracene in 1,2-dichloroethane have been determined. Possible factors responsible for the sharp difference between the volumes of activation and reaction are considered.     

Studying the effect of high pressure on the cycloaddition reactions of maleic anhydride and substituted anthracenes

The kinetics (rate, activation, and volume) of the high-pressure (up to 2500 bar) Diels-Alder reactions of maleic anhydride with 9-phenylanthracene and 9,10-dimethylanthracene in toluene is investigated.     

Effect of the initial maleic anhydride content on the grafting of maleic anhydride onto isotactic polypropylene

A series of ¹³C‐enriched maleic anhydride grafted isotactic polypropylene samples were prepared in solution at 170 °C by changes in the initial maleic anhydride content. The NMR spectra of the samples showed that the signals of the maleic anhydride attached to the tertiary carbons of the isotactic polypropylene chains increased considerably with increasing maleic anhydride content, whereas the signals of the maleic anhydride on the radical chain ends (with a single bond) arising from β scission did not. On the other hand, the signals of the maleic anhydride on the radical chain ends with double bonds increased markedly with increasing maleic anhydride content, and this suggested that β scission could occur extensively after maleic anhydride was attached to the tertiary carbons. As a result, the molecular weight of the grafted polypropylene decreased significantly with increasing maleic anhydride content in this study. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5529–5534, 2005     

热重法测定高马来酸酐含量苯乙烯-马来酸酐共聚物的组成

高马来酸酐含量苯乙烯-马来酸酐共聚物(SMA)是一种具有优良耐热性、刚性和尺寸稳定性的新型高分子材料.由于SMA分子中含有极性很强、反应活性很高的酸酐官能团,所以它被广泛应用于涂料、粘合剂的改性剂、地板抛光的乳化剂、复合材料和颜料的分散剂、水处理剂等领域[1-5].     

Solvent effect on the rate of cycloaddition of isoprene to maleic anhydride

The solvent effect on the rate of the reaction of isoprene with maleic anhydride was studied; the total effect of the solvent polarity and cohesion energy density was revealed.