第29卷第4期武漢工程大學(xué)學(xué)報Vol 29 No 42007年07月文章編號:1004-4736(2007)04-0008-03二對甲苯磺酸乙二醇酯的合成與表征李慶祥*,沈云軍(武漢工程大學(xué)化工與制藥學(xué)院,湖北省新型反應(yīng)器與綠色化學(xué)工藝重點(diǎn)實驗室,湖北武漢430074)摘要:以對甲苯磺酰氯和乙二醇為原料合成了二對甲苯磺酸乙二醇酯,采用紅外光譜和元素分析對其進(jìn)行了表征,并用Ⅹ-射線晶體衍射的方法測定了其晶體結(jié)構(gòu),該晶體屬于單斜晶系,C2/c空間群,晶胞參數(shù)a=1.07138(17)mm,b=1.03680(16)mm,c=1.5703(2)nm;每個晶胞中所含分子數(shù)z=4,晶體密度計算值Dak=1.4llg/cm3,整個分子結(jié)構(gòu)呈“蝙蝠”狀,分子間存在C-H…O弱相互作用.紅外光譜和元素分析與實驗結(jié)果一致關(guān)鍵詞:乙二醇;對甲苯磺酰氯;二對甲苯磺酸乙二醇酯;晶體結(jié)構(gòu)中圖分類號:O623.42+6.1文獻(xiàn)標(biāo)識碼:A0引言1.3結(jié)構(gòu)表征產(chǎn)品取樣,分別在240C型元素分析儀和二對甲苯磺酸乙二醇酯是一種重要的有機(jī)中1 mpact420型紅外光譜儀上對樣品進(jìn)行元素分析間體,廣泛用于含氮大環(huán)化合物的合成與橋和紅外光譜測定(KB壓片)聯(lián).本研究以乙二醇和對甲苯磺酰氯為原料1.4晶體結(jié)構(gòu)的測定合成了二對甲苯磺酸乙二醇酯,用Ⅹ射線晶體衍選取一顆大小為0.3mm×0.2mm射的方法測定了它的晶體結(jié)構(gòu),并采用紅外光譜0.2mm的單晶(適合X-射線結(jié)構(gòu)分析的單晶由和元素分析對萁進(jìn)行了表征·二對甲苯磺酸乙二該化合物的乙醇溶液在室溫下緩慢揮發(fā)得到)用醇酯的合成路線如下于結(jié)構(gòu)分析,在 SMART APEX-CCD單晶衍射0-10℃儀上,于292(2)K下用MoKa射線HOCH, CH,OH+ 2TSClTSOCH, CH,OTs+ 2HCI(λ=0.071073mm),以ga掃描方式在(Ts: CHiSO.-)5.20≤20≤56.00°內(nèi)共收集5055個衍射點(diǎn),其1實驗部分中1898個(Rm1=0.0702)獨(dú)立衍射點(diǎn),1563個Ⅰ>2σ(1)的可觀察衍射點(diǎn)用于結(jié)構(gòu)分析和結(jié)構(gòu)修1.1試劑與儀器正,全部數(shù)據(jù)經(jīng)Lp因子和經(jīng)驗吸收校正.晶體結(jié)乙二醇、對甲苯磺酰氯、甲苯、三乙胺和無水構(gòu)采用 SHELXS97程序由直接法解出.對氫原乙醇均為分析純試劑.子和非氬原子分別采用各向同性和各向異性熱參240C型元素分析儀,美國P-E公司; Impact數(shù),用全矩陣最小二乘法進(jìn)行結(jié)構(gòu)修正,精修采用420型紅外光譜儀,美國 Nicolet公司; SMART SHELXI97程序完成APEX-CCD單晶衍射儀,德國 Bruker公司1.2二對甲苯磺酸乙二醇酯的合成(612結(jié)果與討論乙二醇5.0g(0.08mol)溶于50mL.甲苯2.1結(jié)構(gòu)表征中,以冰水浴冷卻至oC后,在攪拌下同時緩緩滴2.1.1元素分析C1H18O3S2,實測值(計算入30.1g(0.16mol)對甲苯磺酰氯的甲苯值)/%:C,52.01(51.88);H,4.87(4.90)(200mL)溶液和19.5g(o.l9mol)三乙胺,滴完2.1.2紅外光譜分析產(chǎn)品的紅外光譜數(shù)據(jù)后在室溫下繼續(xù)反應(yīng)3h,蒸干甲苯,得到的白色(KBr壓片,cm-1):2993.72,2956.05,2923.77,固體用水洗滌三次,無水乙醇重結(jié)晶,得白色晶體1595.28,1451.79,1363.65,1181.39,777.6224.91g,收率83.4%,熔點(diǎn)119~120C紅外光譜分析表明:產(chǎn)品結(jié)構(gòu)中存在苯環(huán)特收稿日期:2007-04-19李慶祥,等:2-二對甲苯磺酸乙二醇酯的合成與表征征吸收峰(77.62,1595.28,1451.79cm-1)、砜甲基碳原子C(1)和磺?；鶊F(tuán)的硫原子S(1)幾乎(S=O)特征吸收峰(1363.65,1181.39cm-1)及與苯環(huán)共平面.原子S(1),O(1),O(2)和C(1)與甲基和亞甲基的特征吸收峰(2993.72,2956.05,苯環(huán)平面C(2)-C(7)之間的距離分別為2923.77cm-1)0.00048,-0.03907,-0.05354和0.0073nm.2.2晶體結(jié)構(gòu)分子中存在兩種C-H……O氫鍵(見表3),這些氫化合物的晶體結(jié)構(gòu)見圖1,部分晶體學(xué)數(shù)據(jù)、鍵可能會使晶體更穩(wěn)定部分鍵長和鍵角數(shù)據(jù)以及氫鍵參數(shù)分別見表1表2二對甲苯磺酸乙二醇酯的部分鍵長、鍵角表2和表3Table 2 Selected bond lengths and bond angles for 1.2化學(xué)鈺鍵長/nm鍵角/(°)C(AHC(1)—C(2)0.1502(3)O(1)-S(1)0.1420(18)C(8)—O(3)O(2)-S(1)O.1422(16C(5)-s(1)0.1747(18)O(3)-S(1)C(3)C(2)—C(1)120.80(2)圖1二對甲苯磺酸乙二醇酯的晶體結(jié)構(gòu)C(7)-C(6)-C(5Fig 1 Crystal structure of 1. 2-bis(p-tolylsulfonatoO(2)-S(1)-O(3)C(4)C(5)-S(1)119.37(14)0(3)-C(8)-C(8)表1二對甲苯磺酸乙二醇酯的晶體學(xué)數(shù)據(jù)O(1)-S(1)—C(5)09.23(10)Table 1 Crystallographic data of 1. 2-bis(pO(1)-S(1)-O(3)108.57(10)lylsulfonato )ethaneC(8)-0(3)-S(1)晶體學(xué)參數(shù)O(2)-S(1)C(5)110.36(9)Empirical formulaCushio s120.15(14)O(1)-S(1)—O(2)119.91(11)Crystal systemO(3)-S(1)-C(5)103.76(8)Symmetry transformations used to generate equivalent atoms0.30×0.20×0.20#1:-x+1,y,-z+3/29 range for data collection /()表3二對甲苯磺酸乙二醇酯的氬鍵1.07138(17)Table 3 Hydrogen Bonds for 1. 2-bis(p-tolylsulfonate1.03680(16)thanec/nmd/nm/ DHA1.7443(5)D-H….4D-HH…4D……4Dak/g·cm-31.411C(7)—H(7)…0(3)#20.0930.2530.3437(3)163.9Absorption coefficient/mm-C(3)一H(3)…0(1)#30.0930.2590.3446(3)153.8F(000)Symmetry transformations used to generate equivaleatomsReflections collected5055Independent reflections1898(Rn=0.0702)#2:x+1/2,y-1/2,z;#3:x,Goodness-of-fit on F參考文獻(xiàn)R,. wR(1> 20(1)0.0469,0.13210.0547,0.1378Largest difference peak[1 Richman J E, Atkins T J Nitrogen analogs of crownId hole/(e·nm-3)32land-220ethers [J. J Am Chem Soc, 1974, 96(7):2268由圖1可知:該化合物分子由兩個對稱部分構(gòu)成一個整體,整個分子呈“蝙蝠”狀,兩個苯環(huán)之2] Atkins T j, Richman J E, Settle WF. Macrocyclic間的二面角為57.0°,遠(yuǎn)小于它的同系物二對甲polyamines: 1, 4, 7, 10, 13hexaazacyclooctadecaneJ] Org Synth,1978,58:86苯磺酸丙二醇酯中的二面角(83.0°81).甲基碳原子C(1)以及磺?；鶊F(tuán)的硫原子S(1)與苯環(huán)平面31 Sessler J I., Sibert J w, Lynch V. Model studiesC(2)C(7)之間的扭轉(zhuǎn)角C(1)-C(2)-C(3)武漢工程大學(xué)學(xué)報[4 Zhang X P, Hsieh W-Y, Margulis T N, et almacrocycles [J]. Inorg Chem. 2000.39(5):881Binuclear copper( I) complexes of bis (1.4.7892triazacyclononane) ligands containing tri-and[6]詹夭榮,宋金明.六對甲苯磺酸甘露醇酯的合成[Jtetramethylene bridging groups. An equilibrium and化學(xué)通報(印刷版),2003,(9):632-635structural study [J. Inorg Chem, 1995. 34(11): [7 Sheldrick G M. SHELXTL V5. 1 Software Reference2883-2888Manual[M]. Madison, Wisconsin, USA: Bruker AXS[5 Brudenell S J Spiccia L Bond A M, et al. StructuralInc,1997.spectroscopic, and electrochemical studies of binuclear [8 Li QX, Shen Y J, Chang LL, et al. Propane-1.3manganese( ) complexes of bis( pentadentatediyl bis(p-toluenesulfonate)[JJ. Acta Cryst. 2006d from bis(1. 4, 7-triazacyclononaneE62:02464-02465Synthesis and characterization of 1, 2-bis(p-tolylsulfonato )ethaneLI Qing-xiang, SHEN Yun-jun(School of Chemical Engineering and Pharmacy, Wuhan Institute of Technologylubei Key Lab of Novel Reactor and Green Chemical Technology, Wuhan 430074, China)Abstract: The title compound, 1. 2-bis(p-tolylsulfonato )ethane, was synthesized from 1, 2-ethandioland p- toluene sulfonylchloride, and was characterized by elemental analysis and IR. And its crystalstructure was determined by X- ray single-crystal diffraction. The results of x- ray single-crystaldiffraction show that the title compound is crystallized in the monoclinic system and C2/ c space group witha=1.07138(17)nm,b=1.03680(16)nm,c=1.5703(2)nm,Z=4,Dak=1.41lg/cm2, The moleculedopts a bat-like conformation and there are weak C-H-O bonds among the adjacent molecules. Thedata of FT-IR and elemental analysis are in accordance with that from the X- ray single- crystalractionKey words: 1. 2-ethandiol; p-toluene sulfonylchloride: 1.2-bis(p-tolylsulfonato )ethane; crystalstructure本文編輯:傳一點(diǎn)(上接第7頁)The effects of iron complexes on the nitration of insulinWANG Tie-lin, CHI Quan, HUANG Kai-xun(1. School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430074, China2. Department of Chemistry, Huazhong University of Science and Technology. Wuhan 430074 China)Abstract: Peroxynitrite anion (ONOO), which is formed in biological systems by the rapid combinationof nitric oxide (NO) and superoxide anion(O-), is a potent and versatile endogenous reactant that canlead to the tyrosine residues of insulin nitration. The effects of several iron complexes on the nitration ofinsulin by peroxynitrite anion were investigated with UV-Vis in vitro, and the factors of the effect on thecatalytic activity of iron complexes were discussed. The present results show that Fe DTPA and ferriccitrate have no obvious effect on the reaction of insulin with peroxynitrite anion, but Fe EDTA cancatalyze the reaction significantly at physiological pH value