資源描述:
《木素的化學構造1》由會員上傳分享,免費在線閱讀,更多相關內(nèi)容在教育資源-天天文庫。
1、第三節(jié)木素的化學構造Chapter3Chemicalstructureoflignin木素的功能基木素的結構單元木素結構單元間的聯(lián)接光譜的基本概念及其在木素結構研究上的應用木素模型構造圖木素-碳水化合物復合體(LCC)一、木素的功能基主要包括甲氧基(-OCH3)、羥基(-OH)和羰基(-CO)。(一)元素組成及甲氧基(methoxylgroup)木素元素分析值/%示性式CHOOCH3云杉MWL64.776.3928.5816.13C9H8.83O2.37(OCH3)0.96山毛櫸MWL60.586.2333.1921.4
2、6C9H8.49O2.86(OCH3)1.43云杉和山毛櫸MWL的元素分析值與甲氧基含量C/H比例比較高,顯示芳香族特性。2甲氧基是木素最重要的特征基團,其含量為:針葉木木素:14%-16%闊葉木木素:19%-22%草本類木素:14%-15%闊葉木木素中甲氧基含量比針葉木高,why?木素中的甲氧基是聯(lián)接在芳香環(huán)上的,而不是聯(lián)接在脂肪族側鏈上。3甲氧基位置的確定甲氧基所處的位置不同,裂開速度不同。是連接在苯環(huán)上還是連接在脂肪族側鏈上?4HowtoanalyzetheMethoxylGroups?Themethoxylcon
3、tentisawidelyusedforcharacterizationoflignins.Itgivesameasureoftheirpurityandoftheirplantorigin.Themethodmostwidelyusedisbasedontheformationofmethyliodidewhenthesampleistreatedwithhydriodicacidatrefluxtemperature.5酚羥基(phenolichydroxylgroup):存在于苯環(huán)上;脂肪族羥基(aliphatic
4、hydroxylgroup):存在于木素結構單元側鏈上。1.酚羥基多數(shù)醚化,少數(shù)游離。(二)羥基(hydroxylgroup)62.脂肪族羥基7使羥基甲基化的試劑硫酸二甲酯重氮甲烷幾乎全部游離羥基甲基化游離的酸性酚羥基甲基化可以測得游離羥基的含量8-碳原子上的-OH處于側鏈上最活潑的部位,制漿化學反應中成為木素和制漿藥液的反應點H9Howtoanalyzethephenolichydroxylgroups?Commoninstrumentalmethodsfortheestimationofphenolicgroupsi
5、nligninarepotentiometricandconductormerictitration,ionizationdifferenceUVspectroscopy,andNMRspectroscopyChemicalmethodsincludedeterminationoftheincreaseinmethoxylcontentafterreactionwithdiazomethane,selectivedeacetylationofacetylatedligninwithaminolysis(氨基水解),and
6、determinationoftheamountofmethanolformedafteroxidationwithsodiumperiodate10Howtoanalyzethephenolichydroxylgroups?(continued)AmoreindirectmethodisbasedonpermangnateoxidationafteralkylationofthephenolicgroupsTheperiodatemethodisbasedontheguaiacylandsyringylstructur
7、eswithaqueoussodiumperiodatetoo-quinonestructureswiththereleaseof1Mmethanolfromeachphenolicunit(Fig.4.27)11Fig.4.2712Howtoanalyzethephenolichydroxylgroups(continued)?Theaminolysisisbasedonthefindingthatphenolicacetatesarecleavedwithpyrrolidine(吡咯烷)muchfasterthana
8、liphaticacetates.ThepyrrolidineacetatesformedinthereactionofanacetylatedligninisdeterminedbyGC(gaschromatography)(Fig.4.28)13Fig.4.2814Howtoanalyzethealiphatic