Kinetically Controlled Regioselective Formation of a Tail-to-Tail Dimer Dianion of 4-(<i>N</i>,<i>N</i>-Dimethylamino)styrene

Warner, William N.; Hogen‐Esch, Thieo E.

doi:10.1021/ma011780e

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“…A similar electron-transfer-mediated regioselective synthesis of a similar butane dianion has been reported for 4-( N , N -dimethylamino)styrene (DMAS) . In that case, this was attributed to the excess of potassium metal that rapidly scavenges any free monomer including any monomer formed by a retroaddition of the trimer dianion.…”

Section: Resultsmentioning

confidence: 56%

“…Other studies have shown that this is related to having a large excess of metal surface or other electron source (Naph •-) during electron transfer to the vinyl monomer and a relatively slow (k 3 , k t ) and perhaps a reversible addition of monomer compared with electron transfer and coupling (Scheme 1). 33 In the present case, the reason for the relatively slow DMVF addition, given the large size of the monomer including the two 9,9-methyl groups, should be predominantly steric rather than electronic.…”

Section: Resultsmentioning

confidence: 68%

“…A similar electron-transfer-mediated regioselective synthesis of a similar butane dianion has been reported for 4-(N,Ndimethylamino)styrene (DMAS). 33 In that case, this was attributed to the excess of potassium metal that rapidly scavenges any free monomer including any monomer formed by a retroaddition of the trimer dianion. This is plausible because the polymerization of the DMAS monomer is insufficiently rapid (at least 1000 times slower than styrene) to lead to significant polymerization, which is presumably due to the electron-rich monomer.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Spectroscopic Studies of Macrocyclic Polystyrene Containing Two Fluorene Units and Single 9,10-Anthracenylidene Group

2009

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The synthesis of narrow distribution model macrocyclic polystyrenes initiated with 1,4-dipotassio-bis-1,4-(9′,9′-dimethyl-2′-fluorenyl)butane (DMFB) containing 12 to 55 styrene units and coupled to a single 9,10-anthracenylidene (AN) unit (PS-DMFB-AN) is reported. The initiator is formed via electron transfer/coupling from potassium naphthalenide to give nearly pure DMFB, followed by the addition of styrene and protonation or intramolecular end-to-end coupling with 9,10-bis(chloromethyl)anthracene to give the linear and cyclic polymers, respectively. Förster transfer from the 9,9-dimethyl-2-fluorenyl (DMF) group donors to the AN groups, surprisingly, only slightly increased with lower degrees of polymerization of the PS segments. Extensive simulations indicate the presence of highly asymmetrical polymers in which the two arms of the polymer dianion significantly differ in the degree of polymerization. This appears to be partially due to chain statistics but also to slow initiation relative to polymerization.

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Section: Resultsmentioning

confidence: 56%

Section: Resultsmentioning

confidence: 68%

Section: Resultsmentioning

confidence: 99%

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