Reactivity of poly(alkoxycarbonylmethylene)s under basic conditions: alkylation of main chain carbon atoms via a ketene silyl acetal-type intermediate and cleavage of the carbon–carbon main chain,Polymer Chemistry

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Reactivity of poly(alkoxycarbonylmethylene)s under basic conditions: alkylation of main chain carbon atoms via a ketene silyl acetal-type intermediate and cleavage of the carbon–carbon main chain
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-12-21 , DOI: 10.1039/d0py01486a
Hiroaki Shimomoto _{1,

2,

3,

4} , Shogo Tsunematsu _{1,

2,

3,

4} , Tomomichi Itoh _{1,

2,

3,

4} , Eiji Ihara _{1,

2,

3,

4}

Affiliation

The reactivities of poly(alkoxycarbonylmethylene)s under basic conditions are described. The reactions of poly(ethoxycarbonylmethylene) (polyEDA′) and poly(benzyloxycarbonylmethylene) (polyBDA′) with a mixture of lithium diisopropylamide and trimethylsilyl chloride transformed a part of the repeating units (ca. 25 and 50 mol% for polyEDA′ and polyBDA′, respectively) into ketene silyl acetal frameworks. The ketene silyl acetal units were partially alkylated by the reaction with a mixture of tetrabutylammonium fluoride (TBAF) and an electrophile (methyl iodide and benzyl bromide), affording poly(substituted methylene)s with quaternary carbon atoms in the main chain, with the highest incorporation of 13 mol% being attained in the methylation of silylated polyBDA′. TBAF was found to effectively cleave carbon–carbon bonds in the main chain of polyEDA′ and polyBDA′ at room temperature for 1 h, yielding poly(alkoxycarbonylmethylene) oligomers with well-defined chain end structures with a much higher frequency of cleavage than that observed with their vinyl polymer counterparts, poly(alkyl acrylate)s.

中文翻译：

聚（烷氧羰基亚甲基）在碱性条件下的反应性：通过乙烯酮甲硅烷基缩醛型中间体使主链碳原子烷基化，并裂解碳-碳主链

描述了在碱性条件下聚（烷氧基羰基亚甲基）的反应性。聚（乙氧基羰基亚甲基）（polyEDA'）和聚（苄基氧羰基亚甲基）（polyBDA'）与二异丙基氨基化锂和三甲基甲硅烷基氯的混合物的反应转化了一部分重复单元（对于polyEDA'和polyBDA'来说分别约为25和50 mol％）分别转化为乙烯酮甲硅烷基缩醛骨架。通过与四丁基氟化铵（TBAF）和亲电子试剂（甲基碘和苄基溴）的反应使乙烯酮甲硅烷基缩醛单元部分烷基化，从而得到主链上具有季碳原子的聚（取代的亚甲基），最高在甲硅烷基化的polyBDA'的甲基化中达到13mol％的结合。发现TBAF在室温下有效裂解polyEDA'和polyBDA'主链中的碳-碳键达1小时，产生具有明确链端结构的聚（烷氧羰基亚甲基）低聚物，其裂解频率比观察到的高得多与它们的乙烯基聚合物对应物，聚（丙烯酸烷基酯）。

更新日期：2021-01-12

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