Novel silicones for transdermal therapeutic system, 5. A novel method of preparation of carboxy‐terminated polydimethylsiloxane and its enhancing effect on transdermal drug penetration
Novel silicones for transdermal therapeutic system, 5. A novel method of preparation of carboxy‐terminated polydimethylsiloxane and its enhancing effect on transdermal drug penetration
复制标题
DOI：
10.1002/marc.1992.030131001
复制
发表时间：
1992-10
期刊：
影响因子：
--
通讯作者：
Y. Nagase;T. Aoyagi;Tomoko Akimoko;T. Fuchikami
中科院分区：
文献类型：
--
作者：
Y. Nagase;T. Aoyagi;Tomoko Akimoko;T. Fuchikami
最近，我们报道了在一个链端含有季盐基团的功能性聚二甲基硅氧烷（PDMS）的制备，其充当表面活性剂x2）。还发现，这些PDMS尤其可用作实用的透皮渗透促进剂，由于PDMS骨架的庞大性和生理惰性，这些促进剂对皮肤无毒。在相同的上下文中，研究了对-（氯甲基）苯乙基封端的PDMS（CMPPDMS）的制备以合成在链末端含有季盐部分的PDMS，因为末端氯甲基在与吡啶衍生物或叔胺反应时可以容易地季铵化。本通讯中，进行CMP-PDMS的另一反应以获得羧基封端的PDMS，其有望成为由硅酮部分组成的新型透皮渗透促进剂。我们认为，在过渡金属催化剂存在下，末端氯甲基的羰基化将适用于提供对-（羧甲基）苯乙基封端的PDMS。这种在一个或两个链端含有羧基的PDMS已经由Kazama等人合成，他们通过六甲基环三硅氧烷（D1）的活性聚合，然后用三甲基甲硅烷基4-（氯二甲基甲硅烷基）丁酸酯（其中羧基被三甲基甲硅烷基单元保护）失活来制备这种功能性PDMS。
Recently, we reported on the preparations of functional poly (dimethylsi1oxane) s (PDMS) containing a quaternary salt moiety at one chain end, which acted as surfaceactive agents' x2). It was also found that those PDMS's could be used, especially, as practical transdermal penetration enhancers which were non-toxic to the skin owing to the bulkiness and the physiological inertness of the PDMS backbone. In the same context, the preparation of p-(ch1oromethyl) phenethyl-terminated PDMS (CMPPDMS) was investigated to synthesize PDMS containing a quaternary salt moiety at the chain end, as the terminal chloromethyl group could be easily quaternized upon reaction with pyridine derivatives or tertiary amines'). In this communication, another reaction of CMP-PDMS is conducted to obtain carboxy-terminated PDMS, which is expected to be a new type of transdermal penetration enhancer composed of a silicone moiety. We thought the carbonylation of the terminal chloromethyl group would be applicable in the presence of a transition metal catalyst, to afford p-(carboxymethy1) phenethyl-terminated PDMS. This sort of PDMS containing the carboxy group at one or at both chain ends has already been synthesized by Kazama et They prepared such a functional PDMS via living polymerization of hexamethylcyclotrisiloxane (D,) followed by deactivation with trimethylsilyl 4-(chlorodimethylsilyl) butanoate, of which the carboxy group was protected by the trimethylsilyl unit.