Autocatalytic Fragmentation of Acetoacetate Derivatives as Acid Amplifiers to Proliferate Acid Molecules
Autocatalytic Fragmentation of Acetoacetate Derivatives as Acid Amplifiers to Proliferate Acid Molecules
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乙酰乙酸酯衍生物的自催化裂解作为酸放大器以增殖酸分子
DOI：
10.1021/ja972353c
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发表时间：
1998
影响因子：
15
通讯作者：
K. Ichimura
中科院分区：
文献类型：
--
作者：
K. Arimitsu;K. Kudo;K. Ichimura
提出了一种新的酸扩散概念，通过提出具有（磺酰氧基）甲基残留物的乙酰乙酸酯的自催化断裂以释放相应的磺酸，从而提高化学放大光刻胶材料的光敏性。设计了2-甲基-2-（（甲烷-或对甲苯磺酰氧基）甲基）乙酰乙酸酯，通过相应的乙酰乙酸进行酸催化裂解，这些乙酰乙酸容易脱羧并随后进行β-消除，得到磺酸，该磺酸可以作为自催化剂导致酸浓度呈几何级数递增。在测试的乙酸酯中，由于其合理的热稳定性，2-甲基-2-（（对甲苯磺酰氧基）甲基）乙酸叔丁基是本实验最合适的试剂。在非极性溶剂和聚[4-(1)叔丁醇-(2)-丁醇-(3)膜中醋酸酯的酸解转化过程中，证实了磺酸的非线性生成。
A novel concept of acid proliferation to improve the photosensitivity of chemically amplified photoresist materials is described by presenting the autocatalytic fragmentation of acetoacetates having a (sulfonyloxy)methyl residue to liberate the corresponding sulfonic acid. 2-Methyl-2-((methane- or p-toluenesulfonyloxy)methyl)acetoacetates were designed to be subjected to the acid-catalyzed fragmentation through the corresponding acetoacetic acids which are readily decarboxylated and undergo the subsequent β-elimination to give a sulfonic acid which can act as the autocatalyst to lead to the increment of acid concentration in geometric progression. Among the acetoacetates tested, tert-butyl 2-methyl-2-((p-toluenesulfonyloxy)methyl)acetoacetate was the most suitable reagent for the present purpose because of its reasonable thermal stability. A nonlinear generation of the sulfonic acid was confirmed in the acidolytic transformation of the acetoacetate in nonpolar solvents and in a film of poly[4-((tert-butox...