4种具有α-季碳结构的对位壬基酚异构体的合成和表征

Synthesis and Characterization of Four para-Nonylphenol Isomers Containing a Quaternary α-Carbon

不同来源工业壬基酚混合物(t-NP)中对位壬基酚(p-NP)异构体的组成各不相同,各异构体之间在环境行为等方面也存在着较大差异,因此在壬基酚的环境归趋、生态毒性以及雌激素活性等研究中迫切需要t-NP中不同单个异构体作为模型化合物,然而目前市场上能购买到的直链壬基酚(4-n-NP)异构体不能作为代表.以苯酚和4种含分支结构的壬醇为原料(苯酚与壬醇摩尔比为4:1),以BF3为催化剂,按照Friedel-Crafts烷基化方法合成了t-NP中常见的4种烷基链具有α-季碳结构的对位壬基酚的异构体,即4(3′,5′-二甲基-3′-庚基)-苯酚(p353NP),4(3′,6′-二甲基-3′-庚基)-苯酚(p363NP),4(2′,6′-二甲基-2′-庚基)-苯酚(p262NP)和4(3′-甲基-3′-辛基)-苯酚(p33NP).合成的壬基酚粗产物用硅胶柱色谱法提纯后的纯度达99%,并经紫外可见分光光度计、荧光分光光度计、HPLC、GC-MS、1H-和13C-NMR进行了表征.合成的4种p-NP异构体可被用于壬基酚的雌激素活性、毒理、代谢和环境归趋等研究.

Isomeric composition of para-nonylpbenol differs among technical nonylphenol mixtures from differem producers and the isomers differ in biological activity and environmental fate. Individual nonylpbenol isomers of the technical mixture are needed for studies on environmental fate, toxicity, and estrogenic activity of nonylphenol. However, the commercial available linear chain nonylphenol 4-n-NP is not a representative of nonylpbenol isomers of the technical mixture. Using Friedel-crafts alkylation, four para-nonylpbenol isomers containing a quaternary α-carbon are synthesized from phenol and four branched nonanols, catalyzed by BF3 at 50℃ in petrol ether solvent. The four isomers are 4-（3＇, 5＇-dimethyl-3＇-heptyl ）phenol （p353NP）, 4-（ 3＇, 6＇ -dimethyl-3＇ -heptyl ）phenol （p363NP）, 4-（ 2＇, 6＇ -dimethyl-2＇ -heptyl ）phenol （p262NP）, and 4-（3＇-methyl-3＇-octyl）phenol （p33NP）. Purification of crude products by silica gel column gave isomers in purity of 99%, which were characterized by means of UV-Vis spectrophotometer, fluorescence spectrophotometer, high performance liquid chromatography （HPLC）, gas chromatography-mass spectrometry （GC-MS）, nuclear magnetic resonance spectroscopy （^1H-and ^13C-NMR）. The four para-nonylpbenol isomers can be applied to studies on estrogenic activity, toxicity, metabolism, and environmental fate of nonylphenol.