二對甲苯磺酸乙二醇酯的合成與表征

第29卷第4期武漢工程大學(xué)學(xué)報ol. 29 No 42007年07月J. Wuhan Inst, Tech,Jul.2007文章編號:1004-4736(2007)04-0008-0二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,湖北省新型反應器與綠色化學(xué)工藝重點(diǎn)實(shí)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(xiàn)晶體衍射的方法測定了其晶體結構,該晶體屬于單斜晶系,C2/c空間群,晶胞參數a=1.07138(17)mm,b=1.03680(16)nm,c=1.5703(2)nm;每個(gè)晶胞中所含分子數Z=4,晶體密度計算值Dk=1.4llg/cm3.整個(gè)分子結構呈“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」實(shí)驗結果一致關(guān)鍵詞:乙二醇;對甲苯磺酰氯;二對甲苯磺酸乙二醇酯;晶體結構中圖分類(lèi)號:O623.42+6.1文獻標識碼:A0引言1.3結構表征產(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(KBr壓片)聯(lián)1-3.本研究以乙二醇和對甲苯磺酰氯為原料1.4晶體結構的測定合成了二對甲苯磺酸乙二醇酯,用Ⅹ射線(xiàn)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構,并采用紅外光譜0.2mm的單晶(適合X射線(xiàn)結構分析的單晶由和元素分析對其進(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(xiàn)如下于結構分析,在 SMART APEX-CCD單晶衍射TOCH CH- OH+2C~010℃儀上,于292(2)K下用MoKa射線(xiàn)TsOCH, CHOTs+ 2HCI(λ=0.071073nm),以ga掃描方式在SO.-)5.20°≤20≤56.00°內共收集5055個(gè)衍射點(diǎn),其1實(shí)驗部分中1898個(gè)(Rmn=0.0702)獨立衍射點(diǎn),1563個(gè)Ⅰ>2σ(1)的可觀(guān)察衍射點(diǎn)用于結構分析和結構修1.1試劑與儀器正,全部數據經(jīng)Lp因子和經(jīng)驗吸收校正.晶體結乙二醇、對甲苯磺酰氯、甲苯、三乙胺和無(wú)水構采用 SHELXS97程序由直接法解出.對氫原乙醇均為分析純試劑子和非氫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,用全矩陣最小二乘法進(jìn)行結構修正,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2二對甲苯磺酸乙二醇酯的合成結果與討論乙二醇5.0g(0.08mol)溶于50mL甲苯2.1結構表征中,以冰水浴冷卻至θC后,在攪拌下同時(shí)緩緩滴2.1.1元素分析C1H1OS2,實(shí)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(0.19mol)三乙胺,滴完2.1.2紅外光譜分析產(chǎn)品的紅外光譜數據后在室溫下繼續反應3h,蒸干甲苯,得到的白色中國煤化工72,2956.05,2923.77,固體用水洗滌三次,無(wú)水乙醇重結晶,得白色晶體CNMHG.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)品結構中存在苯環(huán)特收稿日期:2007-04-19基金自然科學(xué)基金(No:20571058);湖北省自然科學(xué)基金(No:2005ABA022)1964-),男,湖北松滋人,副教授,博士.研究方向:生物無(wú)機化學(xué).*通訊聯(lián)系人李慶祥,等:2-二對甲苯磺酸乙二醇酯的合成與表征征吸收峰(777.62,1595.28,1451.79cm-1)、砜甲基碳原子C(1)和磺?；鶊F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923.77cm-1)0.00048,-0.03907,-0.05354和0.0073nm2.2晶體結構分子中存在兩種C—H…O氫鍵(見(jiàn)表3),這些氫化合物的晶體結構見(jiàn)圖1,部分晶體學(xué)數據、鍵可能會(huì )使晶體更穩定部分鍵長(cháng)和鍵角數據以及氫鍵參數分別見(jiàn)表1表2二對甲苯磺酸乙二醇酯的部分鍵長(cháng)、鍵角表2和表3Table 2 Selected bond lengths and bond angles for 1, 2bis(p-tolylsulfonato )ethane化學(xué)鍵鍵長(cháng)/mm鍵角/()C(AlC(1)—C(2)0.1502(3)CaLO(1)-S(1)0.1420(18)C(8)—O(3)的0.1422(16C(5)-S(1)0.1582(15)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構(7)-C(6)-C(5)119.09(19)Fig. 1 Crystal struc103.67(9(4)C(5)-S(1)119.37(1thandO(3)-C(8)—C(8)107.13(16)表1二對甲苯磺酸乙二醇酯的晶體學(xué)數據O(1)-S(1)-C(5)109.23(10Table 1 Crystallographic data of 1.2bis (pO(1)-S(1)O(3)108.57(10)tolylsulfonato )ethaneC(8)-0(3)-S(1120.07(13)晶體學(xué)參數數據O(2)-S(1)—C(5110.36(9)rmulaChiSo szC(6)-C(5)—S(1)20.15(14)O(1)-S(1)-O(2)119.91(11)MonoclinicO(3)-S(1)—C(5)103.76(8)ColorlessSymmetry transformations used to generate equivalent atoms#1:-x+1,y,-z+3/2range for data collection /()2.59~26.9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-tolylsulfonato)1.03680(16)1.57030(2)1.7443(5)D—H….4D-HH…AD…A/(°)al/g·cmC(7)—H(7)…0(3)#20.0930.2530.3437(3)163.9Absorption coefficient /mm -C(3)H(3)…O(1)#30.0930.2590.3446(3)153F(000)Symmetry transformations used to generate equivalent atordent reflections1898(Rm=0.0702)Goodness -of -fit on F1.087參考文獻R1,tR2(l>20(10.0469,0.1321RI, wR,(all data)0.0547,0.1378[1 Richman J E, Atkins T J Nitrogen analogs of crown32land-220nd hole/(e·nm-3)ethers [J. J Am Chem Soc, 1974, 96(7):2268由圖1可知:該化合物分子由兩個(gè)對稱(chēng)部分T I. Richman I E, Oettle W F. Macrocyclic構成一個(gè)整體,整個(gè)分子呈“蝙蝠”狀,兩個(gè)苯環(huán)之中國煤化工7,10.13,16間的二面角為57.0°,遠小于它的同系物二對甲CNMHGJT. Org Synth, 1978, 58: 86苯磺酸丙二醇酯中的二面角(83.08).甲基碳原子C(1)以及磺?；鶊F的硫原子S(1)與苯環(huán)平面31 Sessler JI. Sibert J W, Lynch V. Model studiesC(2)C(7)之間的扭轉角C(1)-C(2)-C(3)related to hemerythrin. Synthesis and characterizationC(4)、S分方數搪5)C(6)C(7)分別為of a bridged tetranuclear iron( I )complex []. Inorg179.72(19)°和178.17(16)°,接近180°,這表明Chem,1990,29(20):4143-4146武漢工程大學(xué)學(xué)報[4 Zhang X P, Hsieh W-Y, Margulis T N, et almacrocycles [J]. Inorg Cherm, 2000,39(5):881Binuclear copper (I complexes of bis(1,4.7triazacyclononane) ligands containing tri-and[6」詹天榮,宋金明,六對甲苯磺酸甘露醇酯的合成[J]tetramethylene bridging groups. An equilibrium and化學(xué)通報(印刷版),2003,(9):632-635.structural 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,1997pectroscopic, and electrochemical studies of binuclear [8 LiQ X, Shen Y J, Chang LL, et al. Propane-1,3manganese( ) complexes of bis( pentadentatediyl bis(p-toluenesulfonate)[J. Acta Cryst, 2006ligands derived from bis(1, 4. 7-triazacyclononaneE62:o2464-02465Synthesis and characterization of 1, 2-bis(p-tol ylsulfonato )ethaneLl Qing-xiang, SHEN Yun-jun(School of Chemical Engineering and Pharmacy, Wuhan Institute of TechnologyHubei Key Lab of Novel Reactor and Green Chemical Technology, Wuhan 430074, ChinaAbstract: 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 singcrystadiffraction 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/cm3. 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-crystaldiffractionKey words: 1, 2- ethandiol; p-toluene sulfonylchloride; 1.2- bis(p-tolylsulfonato )ethane; crystal本文編輯:傳一點(diǎn)(上接第7頁(yè))The effects of iron complexes on the nitration of insulinWANG Tie-lin, CHI Quan, HUANG Kai-run(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 ChinaAbstract: Peroxynitrite anion (ONOO), which is formed in biological systems by the rapid combinationof nitric oxide(NO)and superoxide anion (0), 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 Ucatalytic activitof iron complexes were discussed. TheH中國煤化工 Actors of the effect on theCNMH Gt Fet DTPAerriccitrate have no obvious effect on the reaction of insulin with peroxynitrite anion, but Fe+ EDTA canatalyze the reaction significantly at physiological pH valueKey words peroxynitrite; insulin; nitration; iron complex本文編輯:傳一點(diǎn)