二对甲苯磺酸乙二醇酯的合成与表征

第29卷第4期武汉工程大学学报Vol 29 No 42007年07月文章编号:1004-4736(2007)04-0008-03二对甲苯磺酸乙二醇酯的合成与表征李庆祥*,沈云军(武汉工程大学化工与制药学院,湖北省新型反应器与绿色化学工艺重点实验室,湖北武汉430074)摘要:以对甲苯磺酰氯和乙二醇为原料合成了二对甲苯磺酸乙二醇酯,采用红外光谱和元素分析对其进行了表征,并用Ⅹ-射线晶体衍射的方法测定了其晶体结构,该晶体属于单斜晶系,C2/c空间群,晶胞参数a=1.07138(17)mm,b=1.03680(16)mm,c=1.5703(2)nm;每个晶胞中所含分子数z=4,晶体密度计算值Dak=1.4llg/cm3,整个分子结构呈“蝙蝠”状,分子间存在C-H…O弱相互作用.红外光谱和元素分析与实验结果一致关键词:乙二醇;对甲苯磺酰氯;二对甲苯磺酸乙二醇酯;晶体结构中图分类号:O623.42+6.1文献标识码:A0引言1.3结构表征产品取样,分别在240C型元素分析仪和二对甲苯磺酸乙二醇酯是一种重要的有机中1 mpact420型红外光谱仪上对样品进行元素分析间体,广泛用于含氮大环化合物的合成与桥和红外光谱测定(KB压片)联.本研究以乙二醇和对甲苯磺酰氯为原料1.4晶体结构的测定合成了二对甲苯磺酸乙二醇酯,用Ⅹ射线晶体衍选取一颗大小为0.3mm×0.2mm射的方法测定了它的晶体结构,并采用红外光谱0.2mm的单晶(适合X-射线结构分析的单晶由和元素分析对萁进行了表征·二对甲苯磺酸乙二该化合物的乙醇溶液在室温下缓慢挥发得到)用醇酯的合成路线如下于结构分析,在 SMART APEX-CCD单晶衍射0-10℃仪上,于292(2)K下用MoKa射线HOCH, CH,OH+ 2TSClTSOCH, CH,OTs+ 2HCI(λ=0.071073mm),以ga扫描方式在(Ts: CHiSO.-)5.20≤20≤56.00°内共收集5055个衍射点,其1实验部分中1898个(Rm1=0.0702)独立衍射点,1563个Ⅰ>2σ(1)的可观察衍射点用于结构分析和结构修1.1试剂与仪器正,全部数据经Lp因子和经验吸收校正.晶体结乙二醇、对甲苯磺酰氯、甲苯、三乙胺和无水构采用 SHELXS97程序由直接法解出.对氢原乙醇均为分析纯试剂.子和非氬原子分别采用各向同性和各向异性热参240C型元素分析仪,美国P-E公司; Impact数,用全矩阵最小二乘法进行结构修正,精修采用420型红外光谱仪,美国 Nicolet公司; SMART SHELXI97程序完成APEX-CCD单晶衍射仪,德国 Bruker公司1.2二对甲苯磺酸乙二醇酯的合成(612结果与讨论乙二醇5.0g(0.08mol)溶于50mL.甲苯2.1结构表征中,以冰水浴冷却至oC后,在搅拌下同时缓缓滴2.1.1元素分析C1H18O3S2,实测值(计算入30.1g(0.16mol)对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红外光谱分析产品的红外光谱数据后在室温下继续反应3h,蒸干甲苯,得到的白色(KBr压片,cm-1):2993.72,2956.05,2923.77,固体用水洗涤三次,无水乙醇重结晶,得白色晶体1595.28,1451.79,1363.65,1181.39,777.6224.91g,收率83.4%,熔点119~120C红外光谱分析表明:产品结构中存在苯环特收稿日期:2007-04-19李庆祥,等:2-二对甲苯磺酸乙二醇酯的合成与表征征吸收峰(77.62,1595.28,1451.79cm-1)、砜甲基碳原子C(1)和磺酰基团的硫原子S(1)几乎(S=O)特征吸收峰(1363.65,1181.39cm-1)及与苯环共平面.原子S(1),O(1),O(2)和C(1)与甲基和亚甲基的特征吸收峰(2993.72,2956.05,苯环平面C(2)-C(7)之间的距离分别为2923.77cm-1)0.00048,-0.03907,-0.05354和0.0073nm.2.2晶体结构分子中存在两种C-H……O氢键(见表3),这些氢化合物的晶体结构见图1,部分晶体学数据、键可能会使晶体更稳定部分键长和键角数据以及氢键参数分别见表1表2二对甲苯磺酸乙二醇酯的部分键长、键角表2和表3Table 2 Selected bond lengths and bond angles for 1.2化学钰键长/nm键角/(°)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)图1二对甲苯磺酸乙二醇酯的晶体结构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1二对甲苯磺酸乙二醇酯的晶体学数据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)晶体学参数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3二对甲苯磺酸乙二醇酯的氬键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参考文献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由图1可知:该化合物分子由两个对称部分构成一个整体,整个分子呈“蝙蝠”状,两个苯环之2] Atkins T j, Richman J E, Settle WF. Macrocyclic间的二面角为57.0°,远小于它的同系物二对甲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)以及磺酰基团的硫原子S(1)与苯环平面31 Sessler J I., Sibert J w, Lynch V. Model studiesC(2)C(7)之间的扭转角C(1)-C(2)-C(3)武汉工程大学学报[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]詹夭荣,宋金明.六对甲苯磺酸甘露醇酯的合成[Jtetramethylene bridging groups. An equilibrium and化学通报(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本文编辑:传一点(上接第7页)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