26325-89-3Relevant articles and documents
1:2-sequence-regulated radical copolymerization of naturally occurring terpenes with maleimide derivatives in fluorinated alcohol
Matsuda, Masaru,Satoh, Kotaro,Kamigaito, Masami
, p. 1774 - 1785 (2013)
Naturally occurring bulky terpenes, such as (+)- and (-)-limonene and (-)-β-pinene, were quantitatively copolymerized with maleimide (MI) derivatives (i.e., phenyl-, cyclohexyl-, ethyl-, and unsubstituted-MI) in PhC(CF3)2OH solvent via selective 1:2-alternating propagation governed by the penultimate effect, which resulted in 1:2-sequence regulated polymers with relatively high glass transition temperatures and optical activities. Similar petroleum-derived bulky olefins possessing cyclohexenyl, cyclohexyl, or additional α-methyl substituents were copolymerized with phenylmaleimide via preferential 1:2-alternating propagation with a slightly lower selectivity. A further decrease in the bulkiness of nonpolar olefins increased the 1:1-alternating sequence. The copolymerization of limonene and acrylonitrile also proceeded approximately via 1:1-alternating propagation, in which the penultimate effect was less observable. Furthermore, when methylene chloride was used instead of fluorinated alcohol for the copolymerization of limonene and phenylmaleimide, the length of the sequence of MI units increased. Thus, in addition to the characteristic MI skeleton, the bulky and rather specific structure of either limonene or β-pinene induces 1:2-selective propagation via the penultimate effect, whereas the fluoroalcohol diminishes the homopropagation of MI via a hydrogen bonding interaction with the MI unit. RAFT copolymerization of limonene and various MI derivatives in PhC(CF3)2OH successfully proceeded to give the end-to-end 1:2-sequence-regulated copolymer with a selective initiating sequence and predominant capping sequence using an appropriate RAFT agent.
Molecules with Twist Bent Bonds. The Synthesis, Properties, and Reactions of trans-Bicyclohept-3-ene and Certain Methylated Derivatives
Gassman, Paul G.,Bonser, Steven M.,Mlinaric-Majerski, Kata
, p. 2652 - 2662 (2007/10/02)
trans-Bicyclohept-3-ene, 7-methyl-trans-bicyclohept-3-ene, and 7,7-dimethyl-trans-bicyclohept-3-ene have been synthesized.Comparison of their ease of oxidation with the ease of oxidation of the analogous cis-bicyclohept-3-enes has been made.Both the thermal and transition-metal complex promoted rearrangements of the trans-bicyclohept-3-enes have been studied.These systems thermally convert to the cis-bicyclohept-3-enes above 100 deg C and are catalytically rearranged at ambient temperature.Trans to cis isomerization alsooccurs at ambient temperature under photoinduced single electron transfer conditions.
Synthesis and Photoinduced Electron-Transfer Promoted Isomerization of 7,7-Dimethyl-trans-bicyclohept-3-ene
Gassman, Paul G.,Mlinaric-Majerski, Kata
, p. 2397 - 2398 (2007/10/02)
The title compound, 1, is highly reactive (very sensitive to acid, and, thermally isomerized to the cis isomer 2, at 110 deg C); photosensitized isomerization of 1 to 2 is effected by the excited state of 1-cyanonaphthalene.
