TY - JOUR
T1 - Tandem GC/MS
T2 - A useful tool for studying end‐capping reactions of oligo(styryl)lithium anions
AU - Brestensky, Donna M.
AU - Hoye, Thomas R.
AU - Macosko, Christopher W.
PY - 1995/9/15
Y1 - 1995/9/15
N2 - Anionic living polymerization methods, using organometallic initiators such as butyllithium reagents, have proven useful for, inter alia, styrene polymerization and are amenable to subsequent functionalization of poly(styryl)lithium in the termination step. In this study, general methods for the selective preparation of small styrene oligomers and termination of the intermediate oligo(styryl)lithium anions were investigated. The crude reaction mixtures were analyzed directly by tandem gas chromatography/mass spectrometry (GC/MS). Of the carbon‐ and silicon‐based electrophiles tested, chloro(chloroalkyl)silanes, Cl‐SiR2(CH2)nCl in particular, were shown by GC/MS to be regioselective end‐capping reagents, thus allowing subsequent transformation to the primary amine. The combined GC/MS data allow not only an estimate of the degree of functionalization, but also the identification of by‐products, thus providing insight into the end‐capping process that otherwise might be difficult to access. © 1995 John Wiley & Sons, Inc.
AB - Anionic living polymerization methods, using organometallic initiators such as butyllithium reagents, have proven useful for, inter alia, styrene polymerization and are amenable to subsequent functionalization of poly(styryl)lithium in the termination step. In this study, general methods for the selective preparation of small styrene oligomers and termination of the intermediate oligo(styryl)lithium anions were investigated. The crude reaction mixtures were analyzed directly by tandem gas chromatography/mass spectrometry (GC/MS). Of the carbon‐ and silicon‐based electrophiles tested, chloro(chloroalkyl)silanes, Cl‐SiR2(CH2)nCl in particular, were shown by GC/MS to be regioselective end‐capping reagents, thus allowing subsequent transformation to the primary amine. The combined GC/MS data allow not only an estimate of the degree of functionalization, but also the identification of by‐products, thus providing insight into the end‐capping process that otherwise might be difficult to access. © 1995 John Wiley & Sons, Inc.
KW - end‐capping reactions
KW - gas chromatography
KW - mass spectrometry
KW - oligo(styryl)lithium anions
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U2 - 10.1002/pola.1995.080331202
DO - 10.1002/pola.1995.080331202
M3 - Article
AN - SCOPUS:84989665800
SN - 0887-624X
VL - 33
SP - 1957
EP - 1967
JO - Journal of Polymer Science Part A: Polymer Chemistry
JF - Journal of Polymer Science Part A: Polymer Chemistry
IS - 12
ER -