Synthesis and Polymerization of an Optically Active Bicyclic Oxalactam. A Novel Hydrophilic Polyamide Membrane Prepared from (+)-(1R,5S)-8-Oxa-6-azabicyclo[3.2.1]octan-7-one
Synthesis and Polymerization of an Optically Active Bicyclic Oxalactam. A Novel Hydrophilic Polyamide Membrane Prepared from (+)-(1R,5S)-8-Oxa-6-azabicyclo[3.2.1]octan-7-one
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光学活性双环草内酰胺的合成和聚合。
DOI：
10.1021/ma60076a003
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发表时间：
1980
期刊：
影响因子：
5.5
通讯作者：
H. Sumitomo
中科院分区：
文献类型：
--
作者：
K. Hashimoto;H. Sumitomo
以（+）-（1H，5S）-8-氧杂-6-氮杂双环[3.2.1]内酰胺为原料，通过阴离子开环聚合制备了一种新型的光学活性亲水性聚酰胺（简称（+）-poly（BOL），2*）。1]以3，4-二氢-2H-吡喃-2-羧酸钠（3）为原料，通过对非对映异构体脱氢松香基铵盐（5）的拆分，合成了辛-7-酮（简写为（+）-BOL，1*）。1* 在二甲基亚砜中的溶液聚合在室温下容易地进行，导致高分子量有规立构聚酰胺2*。分别在约290-305和330 ℃观察到由于2* 的熔融和分解引起的热转变，其高于由外消旋BOL制备的聚酰胺的热转变。2* 的吸湿性一定是由于酰胺键和四氢吡喃环沿着聚合物链的一些有规立构排列，这可能形成被非极性疏水微区包围的极性亲水微区。2* 的亲水膜容易通过从聚合物在2，2，2-三氟乙醇-氯仿中的溶液浇铸而获得。该膜表现出更好的分数溶质排斥在其水溶液中，连同高的水渗透性，比膜从外消旋BOL。开拓性的工作由Hall 1，2上的一些bicycliclactams的合成和它们的聚合性是众所周知的。在以前的文献3，4中，我们报道了一类新的外消旋双环内酰胺8-氧杂-6-氮杂双环[3.2]在室温或低于室温下的阴离子开环聚合。1]辛-7-酮（简写为BOL，1），得到新型高分子量聚酰胺，聚（四氢吡喃-2，6-二亚氨基羰基）（聚（BOL），2）。
Anovel optically active hydrophilic polyamide (referred to as (+)-poly (BOL), 2*) was prepared by the anionic ring-opening polymerization of an optically active bicyclic oxalactam,(+)-(lfi, 5S)-8-oxa-6-azabicyclo [3.2. 1] octan-7-one (abbreviated as (+)-BOL, 1*), which was synthesized from sodium 3, 4-dihydro-2if-pyran-2-carboxylate (3) through the optical resolution of its diastereomeric dehydroabietylammonium salt (5). Solution polymerization of 1* in dimethyl sulfoxide proceeded readily at room temperature, leading to the high molecular weight stereoregular polyamide 2*. Thermal transitions due to fusion and decomposition of 2* were observed at about 290-305 and 330 C, respectively, which were higher than those for the polyamide prepared from racemic BOL. The hygroscopic properties of 2* must result from some stereoregular arrangement of an amide linkage and a tetrahydropyran ring along the polymer chain, which may form polar hydrophilic microdomains surrounded by nonpolar hydrophobic microdomains. The hydrophilic membrane of 2* was easily obtained by casting from a solution of the polymer in 2, 2, 2-trifluoroethanol-chloroform. The membrane exhibited better fractional solute rejection in its aqueous solution, together with high water permeability, than the membrane from racemic BOL.Pioneering work by Hall1, 2 on the syntheses of a number of bicycliclactams and their polymerizabilities is wellknown. In preceding papers, 3, 4 we have reported the an-ionic ring-opening polymerization at or below room tem-perature of a new class of racemic bicyclic oxalactam, 8-oxa-6-azabicyclo [3.2. 1] octan-7-one (abbreviated as BOL, 1), leading to a novel high molecular weight polyamide, poly (tetrahydropyran-2, 6-diyliminocarbonyl)(poly (BOL), 2).