0000000000388130
AUTHOR
Shadpour Mallakpour
Step growth polymerization via tandem ene and diels-alder reactions
In contrast to other electron deficient enophiles or dienophiles which react with 1,4-cyclohexadiene (1,4-CHD) under aromatization, 1,2,4-triazoline-3,5-diones react in a defined reaction sequence. In a first step the 1,4-cyclohexadiene reacts via an ene-reaction. The intermediately formed substituted 1,3-cyclohexadiene immediately reacts in a Diels-Alder reaction. The regiochemistry of the Diels-Alder reaction is controlled by the solvent polarity. This reaction sequence can be used to synthesize polymers. Low-molar-mass model compounds were synthesized to elucidate the stereochemistry of the polymers. By varying the bistriazolinedione, polymers with backbones of different rigidity are ava…
Step-growth Polymerization ofBistriazolinediones with1,1-Diphenylethylene
The reactions of 4-ethyl-1,2,4-triazoline-3,5-dione (ETD) (1) and 4-phenyl-1,2,4-triazoline-3,5-dione (PhTD) (2) with 1,1-diphenylethylene (DPE) (3) were investigated at room temperature. The reactions are very fast and are completed in less than 4 min. These reactions lead to the formation of two 2 :1 adducts via double Diels-Alder and Diels-Alder-ene reactions in a ratio of 1.35 : 1. The structure of these adducts where R = Et were determined by X-ray analysis of a single crystal. These compounds were used as models for the polymerization reactions. The reaction of bistriazolinediones (1,6-bis-(3,5-dioxo-1,2,4-triazoline-4-yl)hexane and bis-(p-3,5-dioxo-1,2,4-triazoline-4-ylphenyl)methane…
Polymerization of Triazolinediones withtrans-3,3-Dichloro-1-phenyl-1-propene
The reaction of 4-phenyl-1,2,4-triazoline-3,5-dione (PhTD) (2) with trans-3,3-dichloro-1-phenyl-1-propene (4) was investigated at room and reflux temperatures in methylene chloride solution. Although the reaction is slow, it gives quantitative yield. This reaction leads to the formation of two 2:1 adducts via double Diels–Alder and Diels–Alder-Ene reactions in a ratio of about 1: 7. The major product was isolated by means of fractional crystallization as a pure compound and was characterized by infra-red (IR), 1H nuclear magnetic resonance (NMR), 13C NMR, mass spectra and elemental analysis. The structure of the minor product was determined by IR and 1H NMR. These compounds were used as mod…