trituratedbeforeuse.Theanalyticaldataareasfollows:HNMR(1ooMHz,CCl):2.25 (s, 3 H), 4.08 (s, 5 H), 4.30 (s, 2 H), 4.61 (s, 2 H); 13C NMR (22.6 MHz) 0: 26.9,69.2,69.5,71.8,79.3,200.1;IR(CCl)cm-1:3100,1675.2. N,N-Dimethylformamide (DMF), 99% (C,H,NO, FW (73.10), mp -61°C, bp153°C, d =0.944, n2p 1.4305)was purchased from Fluka ChemieAG, and usedwithout further purification.CAUTION:DMF is a cancer suspect agent.3. The best results were obtained in an argon atmosphere, although from thestability of theproduct it seemsmost likelythat an inertgas atmosphere is notessential.Caremustbetakentostirtheentiresystem,particularlyforlarge-scalesyntheses.4.Phosphorusoxychloride(POCl),99%(FW153.33,mp1.25°C,bp105.8°C,d=1.645)available fromFluka Chemie AG, was used as purchased.POCl is highlytoxic and moisture sensitive.5. CAUTION: The formation of the complex is highly exothermic! Be aware of thehazards of phosphorus oxychloride6. This is a safety measure in case the neutralization should become tooexothermic.7. If the ethereal layer turns orange, it is removed and replaced with 75 mL offresh ether. This procedure removes any traces of unreacted acetylferrocene orferroceneimpurities.Theuseofapipetteisrecommendedto replacetheorganiclayer,ifnecessary.8. Sodium acetate trihydrate (CH,cO,Na : 3 Ho) 99%, available from FlukaChemie AG, was used.Anhydrous sodium acetate (CH,CO,Na)99% is onlyappropriate,if sufficientamounts of waterarepresent.9. Initially the phase separation is hard to discern. Extraction is continued untiltheorganicphaseisnearlycolorless.1o.Additional sodium acetate trihydrate is added to thecombined aqueousphases, which after some time, affords a small amount of additional product uponether extraction. Careful extraction and washing of the organic phases preventsundesired polymerization.Theyield and quality oftheproduct obtained are largelydependent on the care taken in the extraction procedure.11. (2-Formyl-1-chlorovinyl)ferrocene (CisH.CIFeO) has the followingspectroscopiccharacteristics:HNMR(300MHz,CDCl):4.24(s,5H),4.57(s,29
triturated before use. The analytical data are as follows: 1 H NMR (100 MHz, CCl4) δ: 2.25 (s, 3 H), 4.08 (s, 5 H), 4.30 (s, 2 H), 4.61 (s, 2 H); 13C NMR (22.6 MHz) δ: 26.9, 69.2, 69.5, 71.8, 79.3, 200.1; IR (CCl4) cm−1 : 3100, 1675. 2. N,N-Dimethylformamide (DMF), 99% (C3H7NO, FW (73.10), mp −61°C, bp 153°C, d = 0.944, n20D 1.4305) was purchased from Fluka Chemie AG, and used without further purification. CAUTION: DMF is a cancer suspect agent. 3. The best results were obtained in an argon atmosphere, although from the stability of the product it seems most likely that an inert gas atmosphere is not essential. Care must be taken to stir the entire system, particularly for large-scale syntheses. 4. Phosphorus oxychloride (POCl3), 99% (FW 153.33, mp 1.25°C, bp 105.8°C, d = 1.645) available from Fluka Chemie AG, was used as purchased. POCl3 is highly toxic and moisture sensitive. 5. CAUTION: The formation of the complex is highly exothermic! Be aware of the hazards of phosphorus oxychloride. 6. This is a safety measure in case the neutralization should become too exothermic. 7. If the ethereal layer turns orange, it is removed and replaced with 75 mL of fresh ether. This procedure removes any traces of unreacted acetylferrocene or ferrocene impurities. The use of a pipette is recommended to replace the organic layer, if necessary. 8. Sodium acetate trihydrate (CH3CO2Na · 3 H2O) 99%, available from Fluka Chemie AG, was used. Anhydrous sodium acetate (CH3CO2Na) 99% is only appropriate, if sufficient amounts of water are present. 9. Initially the phase separation is hard to discern. Extraction is continued until the organic phase is nearly colorless. 10. Additional sodium acetate trihydrate is added to the combined aqueous phases, which after some time, affords a small amount of additional product upon ether extraction. Careful extraction and washing of the organic phases prevents undesired polymerization. The yield and quality of the product obtained are largely dependent on the care taken in the extraction procedure. 11. (2-Formyl-1-chlorovinyl)ferrocene (C13H11ClFeO) has the following spectroscopic characteristics: 1 H NMR (300 MHz, CDCl3) δ: 4.24 (s, 5 H), 4.57 (s, 2 9
H),4.75 (s,2H),6.40 (d,1 H,J =6.7),10.09 (d,1 H,J = 6.7);IR (CCl) cm-1:2851,1671.12.1,4-Dioxane,99%(C.H.0z,Fw(88.11),mp11.8°C,bp100-102C,n2op1.4225,d =1.034) was purchased from Aldrich Chemical Company,Inc.anddistilledfromsodiumbenzophenoneketylbeforeuse.CAUTIOoN:dioxaneisacancersuspectagentandaflammable liquid.Attemptstouseothersolventsfailed,anddespite subsequent addition of aqueous sodium hydroxide, prior distillation of thedioxanefrom sodiumbenzophenoneketyl seems to be essential.13.Asolutionof aqueoussodiumhydroxideispreparedbydissolving10gofsodium hydroxide pellets, 97% (Fluka Chemie AG) in 250 mL of water. The solutionisheatedto boilingbeforeaddition.14. After this time, TLC analysis (hexane as eluent) indicates essentially completeconversion to ethynylferrocene and an impurity with an R, value near zero.15.A pH of 6-7 should be maintained.The phase boundary of the organic andaqueousphasesisoftendifficulttodiscern,butseparationismostsatisfactoryiftheorganic/aqueous mixture is filtered through a pad of Celite to remove an oily thirdphase prior to separation of the aqueous and organic layers.After the finalextraction,the organiclayershould benearlycolorless.16.Silica Gel 60741 from Fluka ChemieAG was used.The impurities remain atthetopofthe5x15-cmcolumnwhenhexaneisusedaseluent.17.The spectroscopicdataforethynylferroceneareas follows:HNMR(30o MHz,CDCl.) O: 2.71 (s, 1 H), 4.19 (m, 2 H), 4.21 (s, 5 H), 4.46 (m, 2 H); 13C NMR (75 MHz)O: 63.5, 68.3, 69.6, 71.2; IR (CCl) cm-: 3311, 2112.WasteDisposalInformationAll toxic materials were disposed of in accordance with "Prudent Practices in theLaboratory";National AcademyPress;Washington,DC,1995.3.DiscussionThe two-step synthesis of ethynylferrocene described here follows essentially thescale-sensitiveroutereportedbyRosenblum,etal.2Althoughvariousintermediateshavebeenevaluated,34(2-formyl-1-chlorovinyl)ferroceneisthemostsuccessfulprecursor inthe synthesis of ethynylferrocene.Treatment of acetylferrocene withphosphorus oxychloride indimethylformamideleadstomixturesof(2-formyl-1-chlorovinyl)ferrocene and themore unstable (1-chlorovinyl)ferrocene,with the ratio of products depending on the stoichiometry.2 However, production of(1-chlorovinyl)ferrocenecanbeeffectivelysuppressedbyemployinganexcessof10
H), 4.75 (s, 2 H), 6.40 (d, 1 H, J = 6.7), 10.09 (d, 1 H, J = 6.7); IR (CCl4) cm−1 : 2851, 1671. 12. 1,4-Dioxane, 99% (C4H8O2, FW (88.11), mp 11.8°C, bp 100–102°C, n20D 1.4225, d = 1.034) was purchased from Aldrich Chemical Company, Inc. and distilled from sodium benzophenone ketyl before use. CAUTION: dioxane is a cancer suspect agent and a flammable liquid. Attempts to use other solvents failed, and despite subsequent addition of aqueous sodium hydroxide, prior distillation of the dioxane from sodium benzophenone ketyl seems to be essential. 13. A solution of aqueous sodium hydroxide is prepared by dissolving 10 g of sodium hydroxide pellets, 97% (Fluka Chemie AG) in 250 mL of water. The solution is heated to boiling before addition. 14. After this time, TLC analysis (hexane as eluent) indicates essentially complete conversion to ethynylferrocene and an impurity with an Rf value near zero. 15. A pH of 6–7 should be maintained. The phase boundary of the organic and aqueous phases is often difficult to discern, but separation is most satisfactory if the organic/aqueous mixture is filtered through a pad of Celite to remove an oily third phase prior to separation of the aqueous and organic layers. After the final extraction, the organic layer should be nearly colorless. 16. Silica Gel 60741 from Fluka Chemie AG was used. The impurities remain at the top of the 5 × 15-cm column when hexane is used as eluent. 17. The spectroscopic data for ethynylferrocene are as follows: 1 H NMR (300 MHz, CDCl3) δ: 2.71 (s, 1 H), 4.19 (m, 2 H), 4.21 (s, 5 H), 4.46 (m, 2 H); 13C NMR (75 MHz) δ: 63.5, 68.3, 69.6, 71.2; IR (CCl4) cm−1 : 3311, 2112. Waste Disposal Information All toxic materials were disposed of in accordance with "Prudent Practices in the Laboratory"; National Academy Press; Washington, DC, 1995. 3. Discussion The two-step synthesis of ethynylferrocene described here follows essentially the scale-sensitive route reported by Rosenblum, et al.2 Although various intermediates have been evaluated,3,4 (2-formyl-1-chlorovinyl)ferrocene is the most successful precursor in the synthesis of ethynylferrocene. Treatment of acetylferrocene with phosphorus oxychloride in dimethylformamide leads to mixtures of (2-formyl-1-chlorovinyl)ferrocene and the more unstable (1-chlorovinyl)ferrocene, with the ratio of products depending on the stoichiometry.2 However, production of (1-chlorovinyl)ferrocene can be effectively suppressed by employing an excess of 10
phosphorus oxychloride. Using dimethylformamide as solvent leads to satisfactoryresultsonlyforsmall-scalepreparations.However,modificationofthestoichiometry and experimental conditions led to the above described procedurewhich is useful for large-scale preparations. Use of conditions employing acomparativelysmallexcessofdimethylformamideandphosphorusoxychlorideresulting in a heterogeneous reaction mixture, as well as use of solid sodium acetatetrihydrate surmount the problems of scale up and enable the removal of organicimpurities.The purity and yield of the intermediate(2-formyl-1-chlorovinyl)ferrocenearesubstantiallyimprovedusingthepresentprocedure,and this intermediate is obtained in pure form without need ofchromatography.The procedure for the final elimination reaction is essentially that of Rosenblum,et al.2 A more detailed procedure is provided which improves reproducibility.Treatmentofanethereal solutionof(2-formyl-1-chlorovinyl)ferrocenewithsodiumamide in liquid ammonia under anhydrous conditions is also an acceptable method,along with the method described which employs base-induced elimination usingaqueous sodium hydroxide in dioxane.z Compounds of the a-haloferrocene typeareconverted more orlessquantitativelyintoalkynesbydehydrochlorination usingpotassiumtert-butoxide in dimethyl sulfoxide.zThisalternativemethod forconvertingtheβ-chloroaldehydemightalsobeuseful,butloweryields(15-20%less)maketheconventionalmethod2moreefficientforthesynthesisofethynylferrocene.Withrespecttocostandeaseofaccessibility,theproceduredescribedaboveissuperior to other, more recent synthetic methods.39112 However, the mostconvenientalternative synthesis of ethynylferrocene is that of Doisneau,et al.11Someprocedures-12alsopermitthesynthesisof1,1'-diethynylferrocenederivatives.Diethynylmetallocenesrepresentversatileprecursorsforthepreparation of oligometallocenes.References and Notes1.Institut fur Allgemeine,Anorganische und Theoretische Chemie UniversitatInnsbruck,Innrain52a,A-6020Innsbruck,Austria.2.Rosenblum,M.;Brawn,N.;Papenmeier,J.;Applebaum,M.J.Organomet.Chem.1966,6,173.3.Benkeser,R.A.;Fitzgerald,Jr.,W.P.J.J.Org.Chem.1961,26,417911
phosphorus oxychloride. Using dimethylformamide as solvent leads to satisfactory results only for small-scale preparations. However, modification of the stoichiometry and experimental conditions led to the above described procedure which is useful for large-scale preparations. Use of conditions employing a comparatively small excess of dimethylformamide and phosphorus oxychloride resulting in a heterogeneous reaction mixture, as well as use of solid sodium acetate trihydrate surmount the problems of scale up and enable the removal of organic impurities. The purity and yield of the intermediate (2-formyl-1-chlorovinyl)ferrocene are substantially improved using the present procedure, and this intermediate is obtained in pure form without need of chromatography . The procedure for the final elimination reaction is essentially that of Rosenblum, et al.2 A more detailed procedure is provided which improves reproducibility. Treatment of an ethereal solution of (2-formyl-1-chlorovinyl)ferrocene with sodium amide in liquid ammonia under anhydrous conditions is also an acceptable method,5 along with the method described which employs base-induced elimination using aqueous sodium hydroxide in dioxane.2,6 Compounds of the α-haloferrocene type are converted more or less quantitatively into alkynes by dehydrochlorination using potassium tert-butoxide in dimethyl sulfoxide.7 This alternative method for converting the β-chloroaldehyde might also be useful, but lower yields (15–20% less) make the conventional method2 more efficient for the synthesis of ethynylferrocene. With respect to cost and ease of accessibility, the procedure described above is superior to other, more recent synthetic methods.8,9,10,11,12 However, the most convenient alternative synthesis of ethynylferrocene is that of Doisneau, et al.11 Some procedures11,12 also permit the synthesis of 1,1'-diethynylferrocene derivatives. Diethynylmetallocenes represent versatile precursors for the preparation of oligometallocenes. References and Notes 1. Institut für Allgemeine, Anorganische und Theoretische Chemie Universität Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria. 2. Rosenblum, M.; Brawn, N.; Papenmeier, J.; Applebaum, M. J. Organomet. Chem. 1966, 6, 173. 3. Benkeser, R. A.; Fitzgerald, Jr., W. P. J. J. Org. Chem. 1961, 26, 4179. 11
4.Schlogl,K.; Egger,H.Monatsh.1963,94,376.5.Schlogl,K.;Steyrer,W.Monatsh.1965,96,1520.6.Bodendorf,K.; Kloss,P.Angew.Chem.1963,75,1397.Abram,T.S.;Watts,W.E.Synth.React.Inorg.Met.-Org.Chem.1976,6,318.Tsuji,T.; Watanabe,Y.;Mukaiyama,T.Chem.Lett.1979,481.This method isnotuseful for thepreparation ofethynylferrocene (expensive;pooryields)9. Negishi, E.-i.: King, A. O.; Tour, J. M. Org. Synth., Coll. Vol. VII 1990, 63.10.Pudelski,J.K.;Callstrom,M.R.Organometallics1992,11,275711.Doisneau,G.;Balavoine,G.;Fillebeen-Khan,T.J.Organomet.Chem.1992,425113.12.Buchmeiser,M.;Schottenberger,H.J.Organomet.Chem.1992,441,45712
4. Schlögl, K.; Egger, H. Monatsh. 1963, 94, 376. 5. Schlögl, K.; Steyrer, W. Monatsh. 1965, 96, 1520. 6. Bodendorf, K.; Kloss, P. Angew. Chem. 1963, 75, 139. 7. Abram, T. S.; Watts, W. E. Synth. React. Inorg. Met.-Org. Chem. 1976, 6, 31. 8. Tsuji, T.; Watanabe, Y.; Mukaiyama, T. Chem. Lett. 1979, 481. This method is not useful for the preparation of ethynylferrocene (expensive; poor yields). 9. Negishi, E.-i.; King, A. O.; Tour, J. M. Org. Synth., Coll. Vol. VII 1990, 63. 10. Pudelski, J. K.; Callstrom, M. R. Organometallics 1992, 11, 2757. 11. Doisneau, G.; Balavoine, G.; Fillebeen-Khan, T. J. Organomet. Chem. 1992, 425, 113. 12. Buchmeiser, M.; Schottenberger, H. J. Organomet. Chem. 1992, 441, 457. 12
实验三新型有机半导体材料的设计、合成、性质及其应用研究指导教师：佟庆笑（一）实验原理本实验以间碘甲苯和间甲基苯胺为起始原料，发生了以铜和配体催化的亲核取代反应，也就是UIlmann缩合反应。反应得到的TMPA中，在N的对位易发生取代反应，得到TBMA.它是本反应的重要中间体。Ullmann反应的应用范围广泛，常用来合成许多对称与不对称的联芳烃衍生物。最常用的芳香碘化物，但漠化物和氯化物甚至硫氰酸酯都可以应用。除铜之外，镍也能使芳香卤化物偶联。反应物环上的取代基对反应的影响很特殊。硝基可以活化反应，但只有邻位的硝基才有活化作用，位于间位和对位的硝基则无活化作用。R和OR基团在所有位置都有活化作用。相反，OH、NH2、NHR、NHCOR、COOH、SO2NH2等基团的存在会阻止反应进行，降低产率。Suzuki反应（铃木反应），也称作Suzuki偶联反应、Suzuki-Miyaura反应，是一个较新的有机偶联反应，零价钯配合物催化下，芳基或烯基硼酸或硼酸酯与氯、溴、碘代芳烃或烯烃发生交叉偶联（常见反应式如下）。这里利用芳基硼酸与溴代芳烃即TBMA发生反应，三种不同的芳基硼酸反应得到三种不同的产品。B(OH)2 +BrF2eqk.cO3aq3 mol-% Pd(PPhs)4benzene,△Sonogashira偶联反应是碘代乙烯或芳香烃与端炔之间经催化生成炔烯化合物的反应。反应催化剂为钯和氯化亚铜，反应需要碱性条件下进行。该反应一般只适用于不饱和碳原子之间的偶合。常见的反应式为：(Ph,P)2PdClR一日Cul, R,NR'R'Pd(PPh)4RRR"R".Cul, Et,NHR"R"实验中利用TMBA与三甲基硅乙炔进行此偶联反应并在碱性条件下得到芳基乙炔为下一步反应做好准备。由共轭双烯与烯烃或炔烃反应生成六元环的反应叫狄尔斯一阿尔德反应（(Diels-Alder反应），又名双烯加成，是有机化学合成反应中非常重要的碳碳键形成的手段之一，如制备含六元环和桥环等各类化合物，也是现代有机合成里常用的反应之一。凡在共轭双烯上有烷基或是烷氧基等压电子基团存在，或在亲双烯物上有氰基，羰基等吸电子基团存在时，进行Diels-Alder反应都比较容易。实验中芳基乙就据此与两种不同的物质反应得到所要的产品。13
实验三 新型有机半导体材料的设计、合成、性质及其应用研究 指导教师：佟庆笑 （一） 实验原理 本实验以间碘甲苯和间甲基苯胺为起始原料，发生了以铜和配体催化的亲核取代反 应，也就是 Ullmann 缩合反应。反应得到的 TMPA 中，在 N 的对位易发生取代反应，得 到 TBMA. 它是本反应的重要中间体。 Ullmann反应的应用范围广泛，常用来合成许多对称与不对称的联芳烃衍生物。最常 用的芳香碘化物，但溴化物和氯化物甚至硫氰酸酯都可以应用。除铜之外，镍也能使芳香 卤化物偶联。反应物环上的取代基对反应的影响很特殊。硝基可以活化反应，但只有邻位 的硝基才有活化作用，位于间位和对位的硝基则无活化作用。R 和 OR 基团在所有位置 都有活化作用。相反，OH、NH2、NHR、NHCOR、COOH、SO2NH2 等基团的存在会阻 止反应进行，降低产率。 Suzuki反应（铃木反应），也称作Suzuki偶联反应、Suzuki-Miyaura反应，是一个较 新的有机偶联反应，零价钯配合物催化下，芳基或烯基硼酸或硼酸酯与氯、溴、碘代芳烃 或烯烃发生交叉偶联（常见反应式如下）。这里利用芳基硼酸与溴代芳烃即TBMA发生反 应，三种不同的芳基硼酸反应得到三种不同的产品。 Sonogashira偶联反应是碘代乙烯或芳香烃与端炔之间经催化生成炔烯化合物的反 应。反应催化剂为钯和氯化亚铜，反应需要碱性条件下进行。该反应一般只适用于不饱和 碳原子之间的偶合。常见的反应式为： 实验中利用 TMBA 与三甲基硅乙炔进行此偶联反应并在碱性条件下得到芳基乙炔， 为下一步反应做好准备。 由共轭双烯与烯烃或炔烃反应生成六元环的反应叫狄尔斯－阿尔德反应（Diels-Alder 反应），又名双烯加成，是有机化学合成反应中非常重要的碳碳键形成的手段之一，如制 备含六元环和桥环等各类化合物，也是现代有机合成里常用的反应之一。凡在共轭双烯上 有烷基或是烷氧基等斥电子基团存在，或在亲双烯物上有氰基，羰基等吸电子基团存在时， 进行Diels-Alder反应都比较容易。实验中芳基乙炔就据此与两种不同的物质反应得到所要 的产品。 13