Recent advance in living anionic polymerization of functionalized styrene derivatives

Hirao, Akira; Loykulnant, Surapich; Ishizone, Takashi

doi:10.1016/s0079-6700(02)00016-3

Cited by 200 publications

(169 citation statements)

References 130 publications

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“…Also notable is the high yield of the electron-deficient 4-cyanoand 3-nitrostyrenes despite their propensity for anionic polymerization. 61 Although the yields may be somewhat lower than those obtained by other methods, they are still above 68% without optimization. Moreover, the goal of identifying inexpensive reagents for the vinylation was accomplished, as the palladium catalyst is now the most expensive component in the reaction.…”

Section: Preparative Vinylation Of Aryl Iodidesmentioning

confidence: 92%

Vinylation of Aromatic Halides Using Inexpensive Organosilicon Reagents. Illustration of Design of Experiment Protocols

2008

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The preparation of styrenes by palladium-catalyzed cross-coupling of aromatic iodides and bromides with divinyltetramethyldisiloxane (DVDS) in the presence of inexpensive silanolate activators has been developed. To facilitate the discovery of optimal reaction conditions, Design of Experiment protocols were used. By the guided selection of reagents, stoichiometries, temperatures, and solvents the vinylation reaction was rapidly optimized with three stages consisting of ca. 175 experiments (of a possible 1440 combinations). A variety of aromatic iodides undergo cross-coupling at room temperature in the presence of potassium trimethylsilanoate using Pd(dba) 2 in DMF in good yields. Triphenylphosphine oxide is needed to extend catalyst lifetime. Application of these conditions to aryl bromides was accomplished by the development of two complementary protocols. First, the direct implementation of the successful reaction conditions using aryl iodides at elevated temperature in THF provided the corresponding styrenes in good to excellent yields. Alternatively, the use of potassium triethylsilanolate and a bulky "Buchwald-type" ligand allows for the vinylation reactions to occur at or just above room temperature. A wide range of bromides underwent coupling in good yields for each of the protocols described.

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Section: Preparative Vinylation Of Aryl Iodidesmentioning

confidence: 92%

Vinylation of Aromatic Halides Using Inexpensive Organosilicon Reagents. Illustration of Design of Experiment Protocols

2008

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“…Both 1 H and 13 C NMR spectra were measured on a Bruker DPX300 in CDCl 3 . Chemical shifts were recorded in ppm downfield relative to CHCl 3 (δ, 7.26) and CDCl 3 (δ, 77.1) for 1 H and 13 C NMR as standard, respectively.…”

Section: Measurementmentioning

confidence: 99%

“…[1][2][3][4][5][6][7] Not only the nonpolar hydrocarbons, such as styrene, α-methylstyrene, 1,3-butadiene, and isoprene, and the cyclic monomers including epoxides and lactones but also polar monomers, such as vinylpyridines, (meth)acrylates, and N,N-dialkylacrylamides, are capable of the living anionic polymerization under the suitable conditions. Furthermore, it has (pK a = 25) [18] in the ketone moieties prohibit the anionic polymerization due to the inherent proton abstraction by basic initiators.…”

Section: Introductionmentioning

confidence: 99%

Living Anionic Polymerization of 1‐Adamantyl 4‐vinylphenyl ketone

Matsuoka

Goseki

Uchida

et al. 2017

Macro Chemistry & Physics

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The anionic polymerization of 1-adamantyl 4-vinylphenyl ketone (1), a styrene derivative carrying an electrophilic carbonyl group, is carried out in tetrahydrofuran (THF). Although no polymerization of 1 occurs with sec-BuLi at −78 °C for 48 h, a polymeric product of 1 is obtained with diphenylmethyllithium in 10% yield under similar conditions. The resulting poly(1) has a very broad molar-mass dispersity (Đ M = M w /M n = 1.72) and a molecular weight higher than the calculated value based on the molar ratio of the monomer and initiator and the conversion. On the other hand, the polymerization of 1 with diphenylmethylpotassium or diphenylmethylcesium quantitatively proceeds in THF at −78 °C within 48 h to form the polymers with predicted molecular weights and narrow molecular weight distributions (M w /M n < 1.1). The stability of the propagating carbanion derived from 1 is demonstrated by the quantitative efficiency of the postpolymerization (sequential monomer addition). The reaction of the adamantyl ketone moieties of poly (1) with methylmagnesium iodide quantitatively proceeds in THF/diethyl ether at room temperature, indicating the high electrophilicity of ketone groups. The resulting poly(1) has a high glass transition temperature at 193 °C, indicating the effect of the bulky adamantyl substituent.

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“…[19][20][21][22] A number of styrene derivatives bearing protected functional groups have been polymerized through anionic polymerization. 19 In general, the hydroxyl and amine groups in styrene are protected by tertbutyldimethylsilylane. 23 Hirao and co-workers pioneered this strategy and showed that the para-substituted styrene undergoes anionic polymerization in a living manner.…”

Section: Introductionmentioning

confidence: 99%

“…They prepared poly-(para-substituted styrene)s with a variety of functional groups such as -OH, -NH 2 , -CHO, -COOH, -CH 2 CH 2 OH, etc. 19 However, noninterfering alkyl-and aryl-substituted styrene undergo anionic polymerization without side reactions in hydrocarbon medium. 24 Zhang and Ruckenstein showed that 4-(vinylphenyl)-1-butene undergoes anionic polymerization without affecting butene pendants.…”

Section: Introductionmentioning

confidence: 99%

Well-Defined Poly(4-vinylbenzocyclobutene): Synthesis by Living Anionic Polymerization and Characterization

et al. 2006

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Living anionic polymerization of 4-vinylbenzocylobutene was performed in benzene at room temperature using sec-butyllithium as the initiator. Results of the kinetic studies indicated the termination-and transfer-free nature of the polymerization. Homopolymers with predictable molecular weights and narrow molecular weight distributions were produced, excluding the interference of the cyclobutene rings during initiation and propagation. Thermogravimetric analysis of poly(4-vinylbenzocyclobutene) in air showed a small weight gain at ∼200°C, a rapid decomposition at ∼455°C, and a gradual decomposition at ∼566°C. This behavior was attributed to the formation of radicals from the pendent benzocyclobutene functionality through o-quinodimethane intermediates and simultaneous decomposition/cross-linking reactions at high temperature. The living nature of the polymerization was also examined via sequential copolymerization with butadiene to form diblock copolymers.

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Recent advance in living anionic polymerization of functionalized styrene derivatives

Cited by 200 publications

References 130 publications

Vinylation of Aromatic Halides Using Inexpensive Organosilicon Reagents. Illustration of Design of Experiment Protocols

Vinylation of Aromatic Halides Using Inexpensive Organosilicon Reagents. Illustration of Design of Experiment Protocols

Living Anionic Polymerization of 1‐Adamantyl 4‐vinylphenyl ketone

Well-Defined Poly(4-vinylbenzocyclobutene): Synthesis by Living Anionic Polymerization and Characterization

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