ÐÏà¡±á>þÿ 46þÿÿÿ389:;<=>?@Ä€ðÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿì¥ÁyÀ ø¿$Pbjbj½½ -Tß{ß{!/ÿÿÿÿÿÿ·rrÌÌÌÌÌÿÿÿÿààà8d|DàÁ"øÀÜœ²²².»Ï¼!¾!¾!¾!¾!¾!¾!$¹#²k&æâ!™ÌÎÎÎâ!ÌÌ²²Û{"öööÎtÌ²Ì²¼!öÎ¼!öör\ TÌ ²ÿÿÿÿÔ9'ðÌÿÿÿÿBÞ° ¨!‘"0Á"¾ Q' rQ'Ì Q'ÌÌ ÜÛ>,öE$ieÛÛÛâ!â!’dÛÛÛÁ"ÎÎÎÎÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿQ'ÛÛÛÛÛÛÛÛÛr ’: Polar Addition to carbon-carbon multiple bonds I. electrophilic addition A. AdE2: AE + AN bimolecular stepwise addition 1. EMBED ChemDraw.Document.6.0 2. addition maybe syn or anti depending on conditions or reagent a. bridging electrophiles will force anti addition b. ion pair formation favors syn addition, show on board c. free ions give mixture (stablized carbocation or polar solvents) for example, halogenation: anti for all alkyl (I2 favored) and less stereospecific for aromatic substitutents (I1 favored) less stereospecific in polar solvents (I1 favored) d. for proton = E+, addition is rate determining and H does not bridge 3. favored by strong electrophiles (CF3SO3H in HOAc) 4. rearrangement competes if cations are unbridged (I1) B. AdE3: AEAN, termolecular concerted addition, reverse of E2 break pð bond, make 2 sð bonds 2. addition is anti 3. mechanism favored when solvent participates (HBr in HOAc) C. Markovnikov's rule: what is it? D. Bromine kinetics: three different mechanisms (three terms!) rate = k1[alkene][Br2] + k3[alkene][Br2][Br-] + k2[alkene][Br2]2 EMBED ChemWindow.Document E. oxymercuration: Nu = water EMBED ChemWindow.Document less electronegative than bromine cation, less sensitive to alkyl inductive effect steric effects more important, attack of terminal is faster than internal alkenes anti and Markovnikov addition is favored II. alkyne addition AdE3 can occur, addition is anti AdE2 generates vinyl cation and non-stereospecific, favored by strong accid EMBED ChemWindow.Document Disubstituted alkynes are bridged by Cl, monosubstituted form vinyl cation EMBED ChemWindow.Document vinyl is resonance stabilized by Cl needed with H but not 2 R Bromination is anti for alkyl substituted and non-stereospecific for aromatic, why? addition of bromide increases anti addition suggesting bromine molecular complex is formed initially (probably in all alkyne brominations) EMBED ChemWindow.Document III. allene addition HX addition, proton addition to center carbon is preferred: conjugated allylic cation (900 out-of-plane) is less stable than vinyl cation EMBED ChemWindow.Document Nucleophiles attacks at 1 position in bromination and oxymercuration EMBED ChemWindow.Document Elimination I. loss of two groups A. að - on same atom B. bð - on adjacent atoms II. extrusion reactions are related to að elimination, i.e. ethylene sulfone (see below) III. bimolecular elimination, E2 mechanism A. AxeDEDN show figure B. concerted, single step reaction, break two bonds make pð bond C. second-order kinetics, first order in base and in substrate D. hydrogen isotope effect is 3-8 indicating loss of H in RDS E. loss of E and N are anti or syn periplanar 1. syn is an eclipsed conformation so anti preferred 2. periplanar elimination allows maximum overlap of newly formed orbitals 3. in cyclic systems such as cyclohexane, only diaxial substituents are periplanar 4. anti-periplanar elimination is also preferred for formation of alkynes F. steric interactions and ion pairing can favor syn elimination G. follow Zaitsev's rule (most substituted double bond formed) if leaving group is negatively charged, Hofmann's rule if neutral (NR3+ or SR2+) (least substituted double bond formed) why? IV. E1, unimolecular mechanism A. DN + DEAxe B. Leaving group leaves first, then base, usually the solvent removes proton C. first-order kinetics D. carbocation leads to competing reactions, SN1 and rearrangements E. loss of stereochemistry unless ion pairing favors formation of olefin before internal rotations can occurs F. Zaitzev's rule is followed if not sterically hindered V. E1cb, carbanion unimolecular elimination A. base removes proton first B. favored by acidic hydrogens bð to poor leaving group loose L C. AxeDE + DN D. mechanism varies depending on relative rates of second step and reverse of first step E. carbanion prefers Z to be a stabilitizing groups: RCO, CN, NO2, SO2R VI. E2C rare A. nucleophile attacks carbon but leaves with proton B. occurs with poor bases but good nucleophiles C. nucleophile stabilizes partial charge on carbon D. rates: tertiary > secondary > primary VII. timing of E and L loss A. L first: carbocation forms, E1 B. E and L at nearly same time: E2 C. E first: carbanion forms, E1cb D. E2 favored by polar aprotic solvents: Zaitsev or Hofmann products depends on conditions and reactants F. strong base favors carbanion formation Elcb G. positive leaving group or very electronwithdrawing groups favor Elcb H. weak base favors E1, strong base E2 or E1cb I. ionizing solvents favor E1 and E1cb J. eliminations often occur from most stable conformations of reactants and intermediates allowed by the mechanism 1. kinetic products are usually obtained 2. gauche or eclipsing interactions are minimized VIII. pyrolytic eliminations /PQUVZ[€Ÿ ¢ C R ™ ¦ È Ê Ë Õ < > ? H [ \ ¸ öìáìáìáìÙÕÊÙì½¯¢½•½¢‡¢½•¢y¢½•y•½j½•½hCghÂ/CJEHOJQJhCgh9xvCJH*OJQJhCghMCJH*OJQJhCgh9xvCJOJQJhCghMCJOJQJhÀ*åhÂ/>*CJOJQJhCghÂ/CJOJQJj©NˆI hMUVhMjhMUhÂ/CJH*OJQJhÂ/CJOJQJhÂ/CJOJQJ$/0Jz£å S ˜ ´ I ‘ Ç ?ýýýõïïã×××Ç³£Ç““õ ÆÐ„˜þdà]„˜þgd^5 Æ „˜þdà]„˜þgd^5 Æ „˜þ„ìdà]„˜þ^„ìgd9xv Æ8„˜þdà]„˜þgd^5 Æ8dàgd^5 ÆÐdàgd^5 ÆÐ Æh¤x¸ ¹ » ¼ ú ý þ ÿ =>?@A .bv H L ñäñä×É×ä¿´¿´¿´¿´¨¿—Š}Š}Šäpäcä\UhCgh®8ŽhCghÂ/hCgh®8ŽCJOJQJhCgh¼|˜CJOJQJhCghž@±CJOJQJhCghž@±CJOJQJ!j–hCghÂ/CJOJQJUhÂ/CJEHúÿOJQJhÂ/CJH*OJQJhÂ/CJOJQJhCgh9xvCJH*OJQJhCgh9xvCJOJQJhCghÂ/CJOJQJhCghÂ/CJH*OJQJ?0ZÖ 2QrÅ@TuÁâ÷ñåÙ×ÑÇÁ»¬¬¬Ù”Ž„h^„h &F Æh &F Æhdàgd^5 &F Æhdàgd^5„ ^„ Æh Æh„Ð^„Ð„8^„8 Æhdàgd^5 ÆÐdàgd^5 ÆÐ Æh¤xL j ž ° ² È Ê Ô Ö ì î ./012DPQRnopqr@VWwxÁÂÞùòëÞÐÞÐÞÐÞÐÞÐÞÐÞÂÞ·Þ£˜·ëÞŽÞ·ë€u·ÞëÞÐÞÐÞ·ëjÕhCghÂ/Uj-”d> hCghÂ/UVhD6ÄCJOJQJj+hCghÂ/U&jo1_: hCghÂ/UVmHnHujhCghÂ/UhCghÂ/CJH*OJQJhCghÂ/CJH*OJQJhCghÂ/CJOJQJhCghÂ/hCgh®8ŽhCgh4cÇ)Þßàáâ-.JKLMrxˆŠÙßðó)klˆ‰Š‹úûZ\”ñæÛÎÇÛÇ³¨Û¡™¡Ç’Ç¡ÇŠÇ†~†g_~†Z†~† hÂ/H*j‘*hÂ/U,jF°’: hÂ/CJOJQJUVmHnHujhÂ/UhÂ/hD6ÄhÂ/>*hCgh”z˜hCghÉ~ˆ>*hCghÉ~ˆju%hCghÂ/U&j[_: hCghÂ/UVmHnHuhCghÂ/hCghÂ/CJOJQJjhCghÂ/Uj hCghÂ/UjÆ”d> hCghÂ/UVâ-€ŒàkŒ¡Xœ*l„†´Ü¾úôúééôãØÖËÅÃÁÁµµdàgd^5„hdà^„hgd^5 Æh &Fdàgd^5 &Fdàgd1l_„^„ &FdàgdÉ~ˆ„h^„h &F”–˜š¬ì*,dfhjl„º¼âä\^x‚„ž¼úþ "$&(*@†´ôìäàÜàäàËÃä¹à¹¯¹¯¹¯¹¡¹”‡”y”j”j”j”]”]hCghž@±CJOJQJhCghÂ/CJEHúÿOJQJhCghÂ/5CJOJQJhCgh7\CJOJQJhCghÂ/CJOJQJhž@±hÂ/6CJOJQJhÂ/CJOJQJhÂ/CJOJQJj8hÂ/U jcj_: hÂ/UVmHnHuhD6ÄhÂ/jhÂ/Uj†1hÂ/Uj`—d> hÂ/UV$BÂ ^`Äa®¯²ó÷·Öä1ñåååÒåÂÂÂ¸²°ªª¢¢ñådàgd^5„h^„h„Ð^„Ð ÆÐ„Ð^„Ð ÆÐ„Ðdà^„Ðgd^5dà„T„&& #$+D€/„´gd^5„hdà^„hgd^5 „hdà¤x^„hgd^5´¶À^_dhi‚ƒ°±óôq{|}ƒ„…°³óæÙÈÙ·œ’ÙÙpÙfZNfZNf=!hahaB*CJOJQJphÿhÂ/CJEHOJQJhÂ/CJEHúÿOJQJhÂ/CJOJQJ!jf]hCghÂ/CJOJQJU!j;ThCghÂ/CJOJQJUhw+fCJOJQJ!hw+fhw+fB*CJOJQJphÿh|VyCJOJQJ!h|Vyh|VyB*CJOJQJphÿ!jð=hCghÂ/CJOJQJUhCghÂ/CJOJQJhCghž@±CJOJQJhCghž@±CJOJQJ³´»½ÚÛßàáãwxüýnt|ÄÆÈ@Bn~ˆŒŽ˜šœž¤¦7öìáìÕìÕìÕìÕìÇì¶¤¶“¶ì‰ììÕìÕìÕìqìgìhCgCJOJQJj×xhÂ/CJOJQJUhÌ}îCJOJQJhÂ/CJOJQJ hCghLCJOJQJmH sH #hCghÂ/5CJOJQJmH sH hCghÂ/CJOJQJmH sH jþkhÂ/CJOJQJUhÂ/CJEHúÿOJQJhÂ/5CJOJQJhÂ/CJOJQJhaCJOJQJ"1I¯üþnÈ€œ *su‚·èEaóóóçßóßóóÑóÅÅ²ßóóóóßdà„õ(„¢& #$+D€/„´gd^5„hdà^„hgd1l_ „hdà¤x^„hgd^5dàgd^5„Ðdà^„Ðgd^5„hdà^„hgd^57>_`jkopsty|ab‚„¥§ÅÉÊÍÏÐÚ34]abc¥©ª«¾ÀÁÎÐÔîäÚäÏäÏäÁä¶ä¨ä¶ä¶ä¶ä¤œ¤˜¤Žä¶äŽä¶äŽä¶ƒvhvh`(Qh`(Q5CJOJQJh`(Qh`(QCJOJQJh`(Q5CJOJQJh1l_CJOJQJh1l_h`(QhÂ/5hÂ/j¦ŒhÂ/CJOJQJUhÂ/5CJOJQJjQˆhÂ/CJOJQJUhÂ/CJH*OJQJhCgCJOJQJhÂ/CJOJQJ!hJDÌhCgB*CJOJQJph(ac…¨Ê3bªÚtÏìd@h@ú@†AèàààÕÉÉÉÉÁµµà©–©©dà„b„„& #$+D€/„´gd^5„hdà^„hgd^5„Ðdà^„Ðgd^5dàgd1l_„hdà^„hgd1l_ Æhdàgd^5dàgd^5„hdà„„,& #$+D€/„´^„hgd^5ÔØÙÚÛõ÷ütì@d@f@ºAêAìAHBJBŠBŒB¼B¾BÀBøBúBüBþB2C4C|C~C¶CôêàÖàËàËàÇÀ¼·¼àµà§à¼Ÿ¼›¼—Œ¼„àsk„àaà„àhÂ/CJOJQJj~«hÂ/U jÄé_: hÂ/UVmHnHujhÂ/Uhëb=hëb=B*phÿhëb=h`(QhÂ/OJQJjFœhÂ/CJOJQJUU hÂ/5hÂ/h1l_hÂ/h1l_hÂ/5CJOJQJh1l_CJOJQJhÂ/CJOJQJh`(QCJOJQJh`(Q5CJOJQJ%A. high temperature >200 C yields syn elimination B. unimolecular, appear to be concerted, probably intimate ion chemistry C. concerted elimination of HX violates symmetry conservation rules? IX. elimination without H A. organometallics with bð hydroxy or alkoxy groups eliminate via a bridged intermediate (M = Hg, Sn, Si) (electrophile catalysis) EMBED ChemWindow.Document B. nucleophile attack on bð-halosilanes also generates alkenes EMBED ChemWindow.Document C. alkene substitution occurs via addition-elimination EMBED ChemWindow.Document X. selected reactions A. pyrolysis of esters, >300 C B. p-toluene sulfonylhydrozones (show resonance forms of dianion) EMBED ChemWindow.Document C. cleavage of cyclic thionocarbonates 7-22 (alternate mechanism with S nucleophile? D. epoxide conversion to olefin E. 7-25, Ramberg-Bäcklund G. alkene addition: HI, HBr, HCl, HF, H2SO4, H2O, ROH, RSH, RCOOH by electrophilic mechanism H. hydrocarboxylation I. epoxidation †AºA¾BC|C¾CD7DMDlDmD¯DÐD%E(EHEJEdEfEÃE÷ïãã×ããÕÌÌÌÃ·Õ±ÕÕÕ©dàgd1l_$gd1l_$„h1$^„hgd1l_„>þ^„>þgd1l_„h^„hgd1l_„8dà^„8gd^5„hdà^„hgd^5dàgd^5dàgd^5¶C¸CºC¼CDD3D4D5D6D:DLDMDlDpDqDŒDD®D¯D°DÌDÍDÎDÏDùDûD$E%E&EïçßÕßÕÄ¼ßÕ±Õ¤Õ™Õ‚xßtiaßÕ¤T¤Õhëb=hÄt@CJOJQJjÆhÂ/Uj±œd> hÂ/UVhÂ/h1l_CJOJQJhëb=hÚ>CJOJQJhÚ>CJOJQJhÂ/6CJOJQJhëb=hÂ/CJOJQJhÂ/5CJOJQJj¿hÂ/U jƒí_: hÂ/UVmHnHuhÂ/CJOJQJjhÂ/UjÆ´hÂ/U j¹ë_: hÂ/UVmHnHu&E'EHEIE\E]EdEeEEŽEE‘E”E•E™E§EÙEÚEëEìEîEïEñEòEôEõE÷EøEúEP PPPPPPPñçÙçËç½ç±ç±ç±ç§ç™ç‹çƒƒƒƒ}yoio^oyh¨H0JmHnHu hñ ³0Jjhñ ³0JUhñ ³Uh¢rojh¢roUj9hÂ/CJOJQJUj›#hÂ/CJOJQJUhÄt@CJOJQJhÂ/CJEHúÿOJQJj´ hÂ/CJOJQJUhÂ/CJOJQJmHsHjôhÂ/CJOJQJUhÂ/CJOJQJj/ÕhÂ/CJOJQJU$ÃEÜEëEíEîEðEñEóEôEöE÷EùEúE P!P"P#P$Pýýýýýýýýýýýýîéýýý$a$$ ÆìHâa$gd¨HCS5, page PAGE 9 13Mar2008 PP"P#P$PüøôêhÂ/CJOJQJh¢rohñ ³h¨H+0°Ð/ °à=!° "° # $ %°°Ð°ÐÐ–Dd |n èèð0² ð #ðAÿð€"ðzÉ¼M>å×Ô ·bð ÿîD9@=ðæzÉ¼M>å×Ô ·bð S(Å³”±AÚÞ´þxÚìÝ?¨ågZð331â‚X)Xl¶Q¬ü³8µ°±!‚àj¡Â4[‡A-¦T[8‹M¥)D˜€È'Ý\»Ý]+‹ñNfLîÜ9÷üyÿ<ïó|>°»Ùd½çþ¾ïûû÷9Ïãœk›Íæ7_ù—k›Í?¼ôßëç6›|c³yçWßýµÍæÚæ{¿óÍk¿þ÷lóußzs³ùû7Îÿóüÿþ‡þÙæûol¾ûw76ç?`óÃ¿ø›Í÷Ïÿõí_ùõ_>ÿŸ~wsc³yó?ÿü/ŸýÏþõüï_Û¼µÙÜø¯_úÍ››³|ûüïžÿÐÍk?þå+þÄõß{ã·ŸýÕÛ×?»ñ×öü¯þ÷úO>}þ2}íÙ¿ß¸~í§~÷¾óÞŸ½ó›ï½ÿÎoÿéwþàO6ÿø·ÿýþ?Ÿÿë_üŸ÷ßøÆþÓ³Ÿùó×ž_Å/\û™]Ï[×Ïÿíú³WýÖ[ïlþíËŸùìõž½Ò7Ÿýó·Ÿý÷g)üô—ÿì{ÿþW¯tó /³@ff#€ÌÌF™™23df6ÈÌl™Ù 3³@ff#€ÌÌF™™23df6ÈÌl™Ù 3³@ff#€ÌÌF™™€uøÿàÁ0®´*Â¿N €À êF0¨…LO-€Ž`P~±YÝkÀ "ü5$x^ô-sDãêpíFÀ“ `|¥#ZŠk:žQƒ‹Àèj\ëðtYïˆ&ä€çÀ°’G0§&×†<‘ÆT="€ie¹f$àY0 ðÌ¬Ìµ$O!€Þµ`rq®1 xþt-DóësíIÀ“ _$Q¢kRž9Š @”*]«ð´èQ‰ê–€ç@óRH«V×¶àÀjQÀ*´½±C8¤`°Íoì ö®E¬E»€ýÊFËÑÇ~`ÊQÀŠ´Ã±Øµx°(MqìvªE¬KkÜê[}®.!E,m#Øþé€ÕÀ`Û>:°:3˜`ÛG"–f ã\ñé€uÀxW€ `Q†0ÀNŸ!ˆX‘N¹¥·èìZKŠXÎ–v¸6yÙÕ·î¼¶–°–+áÚäÕV—]@érRÀBvlk“×Ùûî *–“"V±{ó[¼Î8l‡P«œ°„}ÛÞzäEöÀ‘û€¥€økxë‘§ß w™+JÁÜêÖ O¿šïrV”"";²ÉAž{'ôÛ9¤**E„Õ¤½Ažu3ŒÙ?d(*EÄÔª±;žu?ŒÜE¬]TŠ¨mK[w<å~˜²—X²®Mf¶îx²-1}G°R]) ”Nmlñd»"È¾`ºR@]ØZã™vE´Ý@èÒR@Z×Zã96Fä=@ÄÒR@cšÖúâ9öFü@¬ÒRÀt#ÛÕúâ öF§ýf'¤.EÌ5¾K)¾ôöèºëì€œÕ¥€‰¦ô§uÄ—Þ!½÷žÍ°º0ËÄÎ´Žøº;dÀ´²˜"¦˜Þ“Ö_q“Û‡6@ªSÀxºÑÚá+î“Ä€Ž¦€Áâô¡µÃ—Û'¶%í‹>#Eë@k‡/´UªmNšU|"† Ø{Ö_h·ÔÜ¢4(÷DŒ¶ë¬¾Ên)¾Q8¼Ö0@ð~³^xü c»px¡' ·øfðø{Æ¦àð*O@W«ô˜5ÂÅ¢[€«K<ý¬Õ]Ö»60GÕw":Y®¯¬v!lcŽ*îD4·y½sZ| ŒG,_lŠhkÝÁˆ-¿¿e˜ä]m½Ö(6E4´ú`ÄS³ñò¾·-ÀÅ¦€VFl¹ë+yã«Ö›"šH3±år¬òøØWÙçÖ t½)àxùÆúßAb·ÛhPÊ‰8RÖV±þ·À«íy€´%§€cänëÏMÛÎ M'à`éÛÃšßsÓ^tÿÛ$á*8‡)ÒÖù–ówM«|p€Rý`ï)!¯~/Ø$j7ûªÖ Ööžr‚;Â !"#$%&'()*þÿÿÿ,-./012Œýÿÿÿ5ýÿÿÿýÿÿÿýÿÿÿýÿÿÿýÿÿÿýÿÿÿýÿÿÿýÿÿÿýÿÿÿBCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~€Root Entryÿÿÿÿÿÿÿÿ5 ÀFÀø9'ðÌ7À[Data ÿÿÿÿÿÿÿÿÿÿÿÿ+JWordDocument4ÿÿÿÿÿÿÿÿ-TObjectPool7ÿÿÿÿ$€ÕÐ9'ðÌÀø9'ðÌ_12336698010ÿÿÿÿ!mºA. 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