شیمی آلی پیشرفته کری انگلیسی

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““ ADVANCED ORGANIC 3 CHEMISTRY Dr. Alireza banaei 

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aie ‏دك كسمم‎ 1. Advanced Organic Chemistry, Part A: “Structure and Mechanisms” Francis A. Carey & Richard J. Sundberg 3" Edition, Plenum Press, 1990. 2 Advanced Organic Chemistry: "Reactions, 1 Mechanisms and Structure” = Jerry March: / 1 0 ۱ ‏ا ل‎ ۱ 07 

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Table of Contents: ‏یر‎ ‏رت‎ 0 Chapter 3: Conformational, Steric, and Stereo Electronic ۴۲۲۵5 ‏لت‎ ‏مع مهد‎ 5: Mel oan oe cco 

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thical Approach to Chemical Bonding 

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Eig Grete Orxpric Okewisiry Our @reus: ‏ل‎ Cs aN a cca aR a NDEs Ce cam Bd NN A 0 PN ANCL La Liat aoe Dac CI: CRN ea a ce ‏ی‎ ‎ee ‏و‎ ا ا لمر ا لان ‎Vee‏ A Cee ee 

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211611112 The Actual molecule is the hybrid of the “Canonical Forms” 

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QOvkevues Led to Cowplex ‏مر‎ ‎۹ ‎A ean ea ca na ‏تس سس را‎ Ga eae aR aeRO ELE ‏ا‎ aS 

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A 1 rig Ethylene: 3(2sp’) —— > Trigonal wb ‎cand‏ ا ا ‎Acetylene: 2(2sp) ——> Linear‏ ‎at-bond ‎۳ ‎ ‎The ‏و‎ ‎ ‎a. banaei ‎Advanced Organic Chemistry (Chapter 1) 

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60 AC Cle Bent bonds (banana type) in cyclo propane ‘eased p ch Advanced Organic Chemistry (Chapter 1) 

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ae Propellanes دكي قل عل [1,11] pmpellane [2,2,2] pmpellane ۳ Angle Strain cause to increased in chemical pee involving CLEAVAGE of the central bond. 

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ee tee Theory (Different Lewis Structure for a Molecule) resent are ON crane oad Nr eta a Nee Rolie rae) race CCT NN Rc a a Neo Te ‏تما‎ ‎NST a ena SL ۲۳ ae UR a ee RL ON eee ee 

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3 ae 8 ‏و‎ ‎WY We WI ۵ ‏ی‎ ‎Oly ‏کر مق لجس‎ Poe ‏سر‎ ‎AS AS WSO‏ لهاك ‎pK,~45 pK,~25‏ ‎ROT cast‏ ا ا ‎Ww WwW Ww ‎ 

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۳ Ww Ww 1 ae ‏وي د‎ 2. _ ۶ gr 1۷ SS 5 Ne 38 Sy major significant minor ‏موه تب سا مس متا‎ Oi cr cs ‏هه‎ cowpourds (ippicdly ot (USS 0 ‏ا‎ 00 > موه و معا 

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Confliction ‎W‏ © ناك 1400 هه ‎NCO‏ ‏0 00 ‎ ‎-hemistry (Chapter 1) 

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Jip Ess ccaslea each 2, Pal cdi petal ia ez esac Bond Lengths (Ay 54 4 46 0-0 142 5 ome ‏هد‎ 6-0 2 47 Cac 20 M. 1 S. Dewar and W. Thie m. Soe. 99:4907 (1977) Table 1.2. values tabu! NT REAL EAN Un caNC acdE rack, ANNI ASNS RANE NUL ae a ۳ C-H gr OCH 7 C-H a. From experiment 

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7۳ مت سس وا وت با و وت مت ما رم ا ‎wolkvue.‏ Homolytic Bond Dissociation Energies Bond Bond Energy (kcal/mol) 04 Advanced Organic Chemistry (Chapter 1) a. banaei 

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AVA Stable Allyl and Benzyl Radicals: AN ‏با م 8 با‎ ‏يق قي حسه لسلسم رآ[‎ OS ee oo ‏سي‎ Sea a ACs as Table 1.4. Heterolytic Bond Dissociation E Some C—H and C—Cl Bonds’ سس ergies for R-H— R*+H R-Cl—R*+C AE es ۳-1 ۱ R (kcal/mol) (keal/mol) BCH, 312.2 CHyCH 272.6 (CH, p>CH 249.9 CH>=CH 290.2 J | I CH.=CHCH: 255.3 / Advanced Organic Chemistry (Chapter 1) 

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‎RO east oe ee ee a}‏ الصا رقم و جوا ‎Table 1. Standard Enthalpies of Form rocarbons kcal/mol” ‎ ‎ 

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aie ‏تا‎ RC ‏هی‎ ‎(u=e-d) Coe grasa TPA NCR ass eas VR CA CRS ccc ۱ cas com ENCANA (Creer hrm (plein Vala (plane Oa 

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0 ‏ان‎ AC al ar al OC ‏:عسات‎ ‎CO a ewan ‏لك ا)‎ ra I Vac Cac NS 1 LESS I Oc a oI OP ARCs a ocd hose شوج مصاعجا 2 صا لجنداع+ا) جز حاصكا(ا) صصص ة) جندكمز3) أددجص لون *) 09 :دواد ة). ‎CaO aoa‏ مس وم ‎a ad‏ ل ل ‎Nc aa Le‏ ما هس و سا موه(« ‎Da a Nd kena‏ ‎ ‎ ‎ 

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1.3 Molecular MOT: Orbits are exteuded over the 7 ۲ ml ate ae لق 0ن ‎Operator‏ 0 Oe (ore Gee CO aren Irganic Chemistry (Chap 

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20700 0 0 0 0 0 93 ‎on Se ae On‏ ل ا ‎(POM a AOl oma ag‏ ‎٩در‎ IN ea coe BD NS ‏مت‎ S| A cee a oad A ‏ا‎ ‏م۱۳‎ ‎For example: Od ae eal eet Be On A Os ‏اا‎ ‎Se Ne) Mie) Mel Macd 7 TOM OM KOR cord Tf ‎ ‎ 

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ابص مگ 3 ا زارت ا 0 0 J. Am. Chem. Soc.; 1975, 97(6), 1319. J. Am. Chem. Soc.; 1975, 97(6), 1338. J. Am. Chem. Soc.; 1975, 97(6), 1347. 0 ٩تا‎ 00000, 000, MOOO!S, G4, . 

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۱ J. Am. Chem. Soc.; 1977, 99(15), 4907. J. Am. Chem. Soc.; 1977, 99(15), 4899. @MOOO/: Jj. Am. Chem. Soc.; 1975, 97(6), 1285. J. Am. Chem. Soc.; 1975, 97(6), ۱۳۷/۹۳۹ (۱ ( ۱ ie Am. Chem. Soc.; 1975, ¢ 97)6(, Hien J. Am. Chem. Soc.; 1975, 97(6), 

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لس و و( ‎eda cad‏ 0 

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ی و ‎emt‏ ستو وا( ‎Ces aa od‏ Por OW, Cy, vert B= 23.6° \ 20 ۵ 40 ‏مكب‎ eo |. ry (Chapter 1) 

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“\—* o (Bonding) Fig. 1.9: Graphic description of combination of two 1s orhitals to give two MO. Ques: Sie etter eyudl to the suc oF the BOs. Ree 0 ‏ا‎ CCAS AACA CRRA CS Ea ca ‏ما ات۳‎ 4 v) Pi elevirous Por cack DO (Bubbau priaviple) 

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تب مت ‎(Antibonding)‏ + سر AS His— >—His His—¢ ‎(Bonding)‏ لا ‎(Bonding)‏ ول ‎Ht BE-61 kcal/mol H, BE=l03kca/mol ‎1 o« Antibonding) Ae (Antibonding) ‏وه ‎ ‎ ‎ ‎(Bonding) / ‎ 

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amor (Antibonding) H1s = ١ 7*1 مز ‎(Bonding)‏ ولا ‎HHe*‏ MO Coury charac Por WWe* ۱ lower woerxp bevels 

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ae ~ Methods Por Covstruvion oP OO Orxpuaws ‎OPE cr‏ ال ا ا ا ‎TS nscale gens)‏ ‎b) Clevioa Gpevirveropy Por Chewird! Ooubsis (EGCO); Bicdicry MC ‏مت مس‎ ‎COO re COS VAC ae ‏اا‎ ‎۱ ‎aC Coa‏ ره ‎ ‎ ‎ 

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Orbital Theory Ortkogooaly oP ot cod ‏م‎ work ke O Gkeletva oP the plover poouyaied sysiews lies in the SCANS IA Les cal Ct pa cael Daca CAO raceme Bn came ca EL pet an eee 0 00 et ۱ ‏ل ا‎ / 

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(ea aoe tae al (Re Rend Venn a csc ۳ 7 ‏هع اكرات‎ E=a +m, jm, =2Cos = [12 m, =2Cos“—* -1802 ‏و20 - بدا‎ -- 8 m, ‏ا‎ =1.247 1, =2Cos-* -- 07 m, Stece =0.445 m, ‏کزوومم-‎ =- 1.804 ‎B,, =(a- 0.448)‏ | | (0+1.802)- رأ ‎ee E., =(2+1.24B) ee E,, =(cr- 1.2478)‏ ‎NSE, =(0 +0446 E,, =(a- 1.8033)‏ ‎ 

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۱ (DE) Por 1,9,0-Merdtriewe wi Qespevt to booded Opstew ‎ae eS a aa‏ ارت ‎ ‎ 

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‎The * OO‏ ی ‎aaa‏ ور ‎r=1 then j=1,2, 2 ‎P=? then j = 1,2, pee ‎1/2 5 [sin 2+1 ‎ ‎ ‎ ‎i n+1 1 7 m, Cc, Cc, C3 ‏الى‎ 2 Ce wy, 1.802 | 0.2319) 0.4179} 0.5211 | 0.5211] 0.4179] 0.2319 ‎0 1.247 | 0.4179 0.5211 | 9 0 > > 5 02319511١79 ‎ ‎ ‎ ‎ ‎ ‎ ‎ ‎w, | 0.445] 0.5211] 0.2319 -| 0.2319] 0.5211 a 0.4179| 0.4179 ‎yw, | -0.445/ 0.5211 3 -| 0.4179] 0.2319 5 3 0.2319] 0.4179 0.5211 w, | -1.247/ 0.4179 -| 0.2319] 0.2319 -| 0.4179 ‎0.5211 0.5211 ‎ ‎ ‎ ‎ ‎ ‎ ‎ 

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‎Oise‏ گس مار ‎AW ‎Unstable Stongly Stable 4nx electron ra fade electron| Planar ‎Conjugated Couto |Antiaromatic Aromatic ‎ ‎ ‎E=a+mp m, =2Cos ‎+(n- 1)/2 for n odd‏ مدز ‎£n/2 for n even ‎ ‎ ‎ 

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a- 26 a- Bp a + ۰+0 0+ 26 7 Cer I we (a cs VO aA 6 LS cas SN Casco a ‏ا لل‎ ea ecm 

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‎a‏ رم( ‎۲( ‏نس 0+ عبر‎ OG =O ‎۱ 0 ae x ‏حري© (ط‎ Leia ko) SM ac 000 - ©( ‎ ‎ 

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WA ‏د‎ a- 0.6186 -- + 0 0+ 6 a + 26 Fig. 1.26: Energy diagram for C3Hg and CH; systems. 0. ‏د 2 :ص0 *وباكج0‎ 2048 tea OG =Op (eons aC am Ki ea) fee OES 5 ‎OC‏ 0 اع د ‎0 ‎ 

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تدان رد" لاه ان لس رد ‎ae Oe ea OS ae‏ ‎leh‏ 

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Double Reaction with Reaction with Bond Electrophiles Nuclephiles Reactive Not reactive Less Reactive Reactive Fig. 1.27: Relative energy of the x andx* orbitals in ethylene and formaldehyde. 

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وت با توا ابیت تارج و ‎LUMO—‏ ‎LUMO—‏ ‎LUMO — 7 |‏ ‎HOMO j W,‏ | ‎HOMO i 1‏ HOMO 4 1 ۳, 1 / / ۱ 0 Ww Ww | ‏ما۷۲‎ 4.0=C—Vile ‏میا‎ | © ول xt MO energy levels with ax-donor substituent. 

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یت 10-۷ ‎LUMO__‏ ‎LUMO — *‏ وس 0۱04 ‎HOMO.‏ ‎HOMO 4 x 7‏ aw 1 اوح سوسوي موسق ‎ALC‏ a MO energy levels with a:x-acceptor substituent. HOMO LUMO \ ‘Fig, 1.29: Orbital coefficient for the HOMO and LUMO of acrolein. J. Am Chem Soc. 95, 4094 (1973) 

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72 ۳ تحص متس مرا ۲ ۲ ااتص مس مسب 

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goog LUMO 1 \ با با ‎ae‏ ,+ يا انا لا / ‎U‏ ا ‎Fig. 30: MOs for ethylene and allyl cation.‏ ‎LUMO of allyl cation ‎bong tna ‏مس شع سجر‎ ‎ 

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م ۱6 همم مه OCA as Gin rast ‏و مس رم متس تا‎ ae Dot oad ناك ناك ۱ -( H © a oN ‏با‎ 2 32 

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Fig 132: Interaction between hydrogen 1s orbitals and carbon 2p, orbitals stabilize the eclipsed conformation of propene. 

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Electron donation from nitrogen lone pair to C-H o* orbital. 3 Ovukuess vP O-W bow prieded vat to the foe pur 

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END OF CHAPTER 

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CHAPTER 2 Stereo Chemical Principle 

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a6 Terms and Definitions stot + 2 5 Stéreoisomers: Constructions with different spatial arrangement. Enantiomers: Stereoisomers that have not super imposable mirror images. Chirality: Property of molecules that have not super 1222053814 mirror images. Homochiral: Samples containing only one enantiomer. Axtvanced Orgsric Crsmistrv (Chapter 2) ee 

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Diastereomers: Stereoisomers that are not Fi enantiomers. Racemic Mixture: Samples containing equal amount of two enantiomer. They show zero net rotation. Conformation: Different molecular spatial arrangement as a result of facile rotation about single bond. Atropisomers: Stereoisomers that rotation about single bond is restricted by steri or other factors. The ۱ ua reo 

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ae 2.1 Enantiomeric Relationship Giga cad Dercqaiude oF Optical ‏مقر(‎ 3) Pewpercure b) Gobet 2) Owe Deceds oP ‏وج بابرا ها‎ Convention: Emission line of sodium lamp at A = 589 nm (Sodium D line) Measured Rotation : [a], | 

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ane Optical Purity OpticalPurity (%) = lmsurot enantiomer, 0 [a ‏ی‎ ‎Enantiomeric Excess: (ee %) ‏ات‎ re xl 0 Where X is Mole Fraction The OP is numerically equivalent to enantiomeric excess. | rr 

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Optical Rotatory Dispersion (ORD): Measurement of rotation as function of wavelength. Use: Specifying the configuration of a molecule by relating it to similar molecules of known configuration. | rr 

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{o] x 16 [a] x10 Fig. 2.1. WY absorption, ORD, and CD curves of ethyl methyl p-tolyl sulfonium tetrafluoroboraie. [Reproduced with permission from J. Org. Chem. 44, 3099 11996).) even orks acura) ere 

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ane Dichroism (CD): Absorption of circularly polarized light by two enantiomers. Circularly polarized light can be obtained by passing plane-polarized radiation through an anisotropic crystal. These materials transmit radiation at different velocities in different directions. 0 = 3330(¢,-e,) e, and e,: Extinction coefficient of the left and right Circularly Polarized Light. Use: CD is quantitatively expressed molecular eke ene uel ica) Beer 

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تن وم مه 2-amino-3-phenyl-l-propanol ten : nee ‏موه‎ oom Fig 22 CDspeciraof($t- andi R)-2-amino-I-phenyt:t- Propanone hydrochloride. (Reproduced from Hel: Chim, Acta 69, 1498 119801.) even orks acura) ‏أعفمقط‎ 

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Specifying The Configuration Oroke-Tagok-Peroy Oowveutiva Ciscker Ovwrctiva Cahn-Ingold-Perlog Convention (R and S description): 1. Sequence Rule: The substituents atoms are assigned decreasing priority in the order of decreasing atomic number. 2. The lowest priority substituent viewed BEHIND the chiral center. ‎e De easing 0 8‏ محا ‎Peet‏ 0 ‎ 

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tits even orks acura) ‏أعفمقط‎ 

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ae Chiral Centers Other Than Carbon ‏مر‎ 1 7 4 1 4 1 ‏بل‎ ‎Q ‏ما‎ ۱ ۳ le 1 ‏م3‎ © go 1 "01 Ok 1 Or ‏اكه‎ be SS ok 2 3 4 5 R 5 Phantom Atom with atomic number zero for tricoordinate chiral centers such as sulfoxides, sulfonium salts and phosphines. 4 \ 3 3 14 2 Oe ۵] ۳ 0 

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Fischer Convention (D and L déscription) for the configuration of carbohydrates and natural substances. Two enantiomers of glyceraldehyde were originally arbitrarily assigned the configuration D and L. This assignment was then confirmed by X-Ray crystallography. مان مو مده مو موه = —10—0 سملم ع رسنس 99 اما ‎CAOW CUOW‏ D-(4)-glyceraldehyde L-()-glyoeraldehyde | rr 

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Rules 1.Major carbon chain align vertically. 2. The most oxidized terminal carbon at the top. 3. The horizontal bonds are directed forward to the viewer. 4.The vertical bonds are directed back, away from the viewer. “oid * ono * ‏'صص' " '' مت‎ ‏و حب أ‎ OW ‏يسم‎ = 10 D-(+-glyceraldehyde L-()-glyoeraldehyde | ۱ 

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eit oo ‏ما‎ CHOW ‏لون رال له‎ C=O ‏ار را‎ wow ‏ملو لون‎ ‏,سول م تس ,سول ما‎ 17-۲ ‏رمسنوه‎ OW ‏سل‎ ‎CHOW ‏ماس‎ CHOW CHOW D-Ribose L-Fucose D-Mannose D-Fructose L COOW Cle CHOW CUCUCT ee L-Alanine L-Serine L-Leucine All amino acids found in proteins have the L - Peruri (Chapter 2) 

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Determination of Configuration on Fischer original molecule has the R configuration ۳ 0 1 22 CHOW enter a curls) erence 

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ral Molecules Having No UP ps 3 ocd -- oO — 0 N WwW ‏را"‎ 4 R(-)-Dimethylallene S(4-Spiro[3,3]-hepta-1,5-diene OO +) ۱ ‏مکی رل‎ ۵ OO ie 3 S(4)-1,1'-Binaphthyl R(+)-1,1'-Spirobiindane | ۱ 

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Determination of Absolute Configuration No direct relationship between the configurational descriptors R and S or D and L and the sign of the optical rotation of the molecule. Approaches: 1. Correlation with the CD and ORD curves of the molecules whose absolute configurations are known. 

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se 2.2 Diastereomeric Relationship 5 ل ‎Diastereomers: Stereoisomers that are not‏ ‎enantiomers.‏ They have different physical and Chemical properties. Snacifirine tha ralativa canfiemratian of turn adiacant 0 ‏مك0 مان مان‎ ‏راو‎ WO AW NO ‏ات با‎ ‏د‎ WO AW W OW MO nl tt OUDW ONOW OUDW CADW D-erythrose L-erythrose D-threose L-threose even orks acura) ۱ 

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Achiral Compounds Containing nmetric Carbon Mesof coo” “COOL SCO ‏ناا عاك‎ Ww OW W OW AW OW WO 1 1 “on 0 ۱ ‏رامین‎ COOW COOW D-tartaric acid L-tartaric acid meso-tartaric acid Syn and Anti: even orks acura ae) ۱ 

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aie Resolution of Enantiomers onverting the mixture of enantiomers into a mixture of diastereomers: Reaction with a pure enantiomer of a second reagent. 2. Kinetic Resolution: Incomplete reaction of two enantiomers with a chiral reagent. 3. Enzymatic Resolution: They are chiral and derived from L-amino acids (making diastereomeric relationship with enantiomers upon interaction). 4. Noncovalent binding with chiral substances 

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qk 0 ' . (UP) (UP), ‏هو مع هیام ثم‎ mixture of enantiomers 2-phenyl-3-methy butanoic acid لد recrystalization from ‘water ane EOH filter cake filtrate ‎a 0‏ ثليه سلجي يليه سلج ‎a‏ مه 9 كما ‎۳ | 0 (UP) (Wf) RC) sy ‎Jj. Org. Chem. 32, 2797 (1967) 

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Kinetic Resolution Senantiomer + Renentiomer | incomplete reaction with an enantiomerically pure reagent مسح كلك if ‏ممتاعمعر عا 6ه علمد‎ 06 <5 if rate of the reaction of R<S. ‘unreacted material enriched in S ‘unreacted material enriched in R product enriched in R product enriched in S 1 ‏ب‎ ‏ا‎ a5 Goats ‏و‎ ‎Ole 4 a RS 5 (R 9/(S S)=1.75 with 0.25 eg. anhydride Bull. Chem. Soc. JPN. 57, 1570 (1984) | 

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Determination of Enantiomeric Purity NMR _ Spectroscopy: Chiral Shift Reagents (making diastereomeric relationship with enantiomers upon interaction) ۸ 000 Mosher's Reagent Perey 

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0 Me PPM Fig. 2.7. NMR spectrum of |-phenylethylamine in the presence ofa chiral shift reagent, showing differential chemical shift of methine and methyl signals and indicating ratio of R- to S-enantio- mers. [Reproduced from J Am. Chem. Soc. 93:5914 (1971) by permission of the American Chemical Society.] eve orks acuta) ‏أعفمقط‎ 

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2.3 Stereochemistry of Dynamic Process Dynamic Stereochemistry: Topological features of processes which affect the molecular shape. Stereo Specific Reaction: Stereomeric starting materials afford stereo chemically different products under same condition. Stereo Selective Reaction: A single reactant has the capacity of forming two Stereomeric products in a particular reaction but one is formed preferentially. Retention of Configuration: A process in which the relative spatial arrangement at the reaction center is the same in the reactant and the product. 

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اا تمس امب اسمسم خا ‎Reurtoa Our prinkats te‏ با «ان يام قر ‎X-Y —» RON! — (Only Avodart)‏ + 55006505 ‎k‏ ‎Qeqivspeviic Qeuvtivg‏ Reyoseevive Rewios! Ove pods if Porwed u ‏مزلم‎ ROWCe + ‏ماما جد بن عع‎ + ROOK x Y wujpr wiuor Reyioselective Qeuvtivog Advanced Organic Chemistry (Chapter 6) a. banaei 

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‎A process which generate both‏ ع د ‎le enantiomers from a single enantiomer.‏ 1 ‎ ‎Epimerization: Occurring the racemization in a single chiral center in a diastereomer. ‎Some Examples for Stereo Specific Reactions: ‎ ‎ ‎Epoxidatin of Alkenes: WO(UL) X4eD)- 0 a0 ‎ASML a Ye) coon WAND, > ‏رلك ملك ناك ‎w‏ ‎2 ‎1 WON) = ۱ CH,CO,0H 7 ‎۷ ‏هک ۵ مر‎ ab ‎ ‎| Pao 

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‎to Dibromocarbene‏ تا ‎ ‎ ‎1 5 ‏باه‎ ‏مد ام قد‎ Yi ۰ —— CHBr, WEA a ‏و006 ...رون‎ ۳ 0 WS. WS. ۲ CHB, ~KOC(CER); Vp, Clo Usd Nuclephilic Substitution (invertion of ۳ th Os ۵ ‏لاك‎ RQ Ke Ot 4 ‏م‎ ‎NaSPh ‎a Bu Ww ‏و‎ ae Bu. ds trans trans cis ‎ ‎even hornets acura) 

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Some Examples for Stereo Selective Reactions Dehydrohalogenation CH,CH,CHCH ‏كا‎ WS | (60%) (20%) + CHjCH,CH=CH, (20%) Addition of Formic Acid to Norbomene | ۱ 

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Addition of Phenoxycarhbene to Cyclohexene 1۸ ‏0م باك رم‎ Os 52 more favorable ne (26%) q ‏را‎ Eee ‏بر 55 نار‎ 5 ‏اد‎ less favorable CW ۳ (14%) Addition to Carbonyl Groups LT | pall ‏مرحي‎ ey fo (90%) (10%) event enter a curls) 

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Cram’s Rule 2g \ “may, ‏ماب‎ ‎exythro (67%) threo (33%) 9 ‏بر للمست‎ hy - / less hindered Nu side R jorge ‏سر‎ ‎Ow ‏هار‎ 1 1 Cle erythro Oe’ 1 1۳ Ok even hornets acura) 

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Racemization a) Cleavage of one ligand and formation of planar in tricoordinate intermediate. b) Pyramidal inversion at trivalent N, S or mpounds. 3 ۲ Rate 5 ‏ی‎ eaiion: Barrier to the inversion process. N containing compounds: The barrier is low Inversion is too rapid The enantiomers can be separated rarely 

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سم Lyk Ube om 5 ‏؛‎ Inversion bamier 8-12 kcal/mol depending on X Cle 0000 No ‏ماو‎ separated | ۱ 

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> Inversion in Heavier Atoms: Higher ‏ام قد‎ Phosphines Or ۰-0 wnt “Bu 32.7 kcal/mol ‏تست‎ ‎Ow ‏مد‎ ‎a “AO كك حت رن | ۱ 

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a6 2.4 Prochiral Relationship “pistinguishing between identical ligands: Enantiotopic Protons AO. iL AO. iL 0 7 a a ~ (R)-1-deutrio-1,3-propandiol (9-1-deutrio-1,3-propandiol Assignment Enantiotopic Protons: Sequence rule, 2 2 AO. 3 3 aces R s 0 5 ( 1 “ler 1# die ) even hornets acura) ۱۳ 

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Enantiotopic protons are equivalent in all chemical and physical respects EXCEPT hacen wl 2 Abin] HARARE OR NS UR WE 0 ‏و کبک‎ 1 The enzyme-catalyzed interconversion of acetaldehyde to ethanol. | ۱ 

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oe Between Two Faces by mzymes or Chiral Chemical Catalysts 0 ‏با"‎ 0 ‏وی‎ Rear ag . 9 RReiethyltartarate ۳ a %@ P متكت مه ‎ie tBuOOH YR‏ ‎MICDOCNs ۲ ۲۳۱۵/۸‏ 3 ‎PUP 5‏ برهتت مد سا ‎COOW‏ با ‎ ‎89 %ee ‎Table 2.1, page 103 ‎even orks acuta} ۱۳ ‎ 

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ae Diastereotopic Ligands aires 1 ‘We, en A2 LOW ase ۰ ۲ 9 Diastereotopic protons in L-phenyl alanine Diastereotopic protons are chemically nonequivalent and can be ۳۳ by phys 1-berzyl-cis(trans)-2,6-dimethylpiperidine اليكو ‎Le‏ ‏۵ يي مات 010000 ؤس مسن سن ‎dk Oe‏ Enantiotopic Protons (singlet) Diastereotopic Protons (AB-Quartet) (molecule is Achiral) (molecule is Chiral (Chapter 2) ‘het event 

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8 > 8 1 2 8 Fig. 2.8. Equivalent benzyl CH; protons in |-benzyl-cis- 2.6-dimethylpiperidine compared with nonequivalent protons in the mans isomer. [Reproduced from Tetrahe- dron 21:2015 (1965) by permission of Elsevier Scicnce.] even orks acuta) 

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END OF CHAPTER 

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mM 3:4°Steric Strain and Molecular Mechanics Fy pain= EU) + EO) + Ele) + E(d) E(): Gretchiay vad cowpresstay pueryy oP stage brads (0): @vud cade dstortics coer وه سوه :)6( CQ): Crary resut Pow worbouded ‏هه‎ even kerk Acuna) ۱ 

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Ope-Oouded Idteruntow: The wost dPPicd codribuics to ee ‏درو‎ Poventiat energy Interaueloar separation Fig. 3.2. Energy as a function of internuclear distance for nonbonded atoms. even heres Mcrae) 

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:عووی و لوا 02-09 ول شا ۳ عرمه وواورن !]1 رل ‎Clo‏ رل ‎A WwW AW‏ را" 1 را" ‎WS‏ را" ‎WwW Yl Ww‏ ‎Clg‏ ما مات ‎G@aucke ati Gaucke‏ ‎Gauche Anti ۸۲۳ =-0.8 kcal/mol‏ Ae 

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& 7۳ + Wy — fant] _19 fant} 219 “< [gauchle 1 [gauchle[ant] 2.9 %lant] =66 %lgauchle=34 even keke Acuna) ۱ 

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Molecules 3.2 Conformations of Ac Reed Dery? unter: Oe-Gtbe: 0.1“ ‏ادو لامها‎ ‏ات۲ ©6. © تي 0ر011‎ أ 0.97 لها مسا ۵ -0 ج 49 :مه لمسا 0 -0 میت باه سا روصت وا م2( :توبات منااق) ‎he hewer habgeus: booger Oud der Drak roti‏ | ۱ 

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‎Prow carbon to‏ ی واه وه ‎boudd to‏ وت وا مان ‏كح دان ‎a‏ ‏2 عار ‎at‏ ‏ی 1 ذا ‎oO‏ ‎Rotational Energy 2. 57 1 56 1.07 kcal/mol‏ ‎Banier ‎Rotational bamier decreases with the number of H/H eclipsing interaction ‎ ‎ ‎even kerk Acuna) 

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عصح9۳) لو 00 © رد ‎Ecllipsed Staggered‏ Dke eclipsed cooPorwutiod is prePerced by about C kodl/cool. MOT: Repusive interaciog betwee the Piled Oe your orbitals cand the Pied 30 orbital oP the double boo. 5 5 “yo ‏ره‎ reduced repulsive major repulsive interaction Interaction. even kerk Acuna) ‏آهد«دط.د‎ 

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Ww B:-0.25 C:175 Relative Stability: B>A >D ~C 

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s-cis skew even kerk Acuna) rrr 

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s-cis (72%) s-trans (28%) Pare even kerk Acuna) 

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3.2 Conformations of Cyclohexane Derivatives اه نار سند للفلل 108 healt | SS kealano| 3 2 3.4. Energy diagram for ring inversion of cyclohexane. [For a rigorous an inversion in cyclohexane, see H, M, Pickett and HL. Strauss, J) Am. Chem, Soc 1281 (1979),] eve here Acura) ‏أعفمقط‎ 

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AG®° =-1800 cal/mol AG? =-RT nKy, == ‏میک‎ 21 == [e] =95%, [axial] =5% ,9=dhaxtal Teteraction even kerk Acuna) ere 

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bow Tewperdure Gtudes get» Opolokexyl ONbride: ‏متام‎ ۰ 190 0 Only equatortdl OocPorwer Oprracric DOR oP Cprtokemd Todide ot -OD °C Fig. 3.6. NMR spectrum of cyclohexyl iodide at —80°C. Only the lowest-ficld signals are shown (100-MHz spectrum). [Reproduced from J. Am. Chem. Soc. 91:344 (1969) by permission of the American Chemical Socicty.] even kerk Acuna) Pruett 

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AG® >-4.5 kcal/mol 9 05 9 I Z wv 16 سس Gs-decaline trans-decaline AG*=12.3-12.4kcalm/mol AH? =-2.7 kcal/mol even kerk Acura) 

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۲ - o* interaction ‏عو‎ ۲ interaction Advanced Organic Chemistry (Chapter 3) 

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| ۱ 

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boat chair boat:boat crown (more stable) boxer Qi (Otexoverd ‏شور‎ Girwtre): tren keri 

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3.5 The Effect of Heteroatoms on Conformational 0 | VV Polar Gubstituect (PP ect: Advanced Organic Chemistry (Chapter 3) ۱ 

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بلاط مره تج ‎Io‏ :و28 ‎@wwer‏ ‏آی هم ‎ot O-(0‏ عون 0۲ i 7 / is Oe strongly favored in CHCl; ۳ ۳ Gover peuvovetste AG is =O) es BO 1 ‏سد‎ 1 Oe ‏عت‎ ‏رام‎ i ‏مه‎ aie GO GO ba ne =- 1.4 kcal/mol K =5 (in50% AcOH/AG,O , 0.1 MH)SOq,, 25°C) Peroni keri istry (Chapter 3) 

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جه سمل رامع ابا اعومظ)- الوم O ۱ ‏چا‎ 0 wl} K =32 (pair liquid, 25 °C) Owetkvxy-Owetkpltetrakydopprode WEL. K =3.4 (in CCl) K =1.8 (in CHxCN) 

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‎oP Buowerto GPPevt:‏ من ‎By Dine ieee cea aera te ren eee ‏سا‎ rere ower varbos is reduced ft uxidl oooh oration (solect ePPeri). ‎b) DOT: @uowerie ePPevt is resutiog Pro ‏مشاه مه‎ betwee pxyyeu LP un the O° orbital DP C-O substitucct. Oked the O-C ۱۳ interuviion is possible. ‎6 ‎— | ‎| — OR Se ‏راومه موسوم وهای ات موه مها واه موم ‎ ‎| Pat 

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Antiperiplanar alignment of the C-X bond with a LP orbital of Ww » ee 50-8 ‎No‏ )0 ”ضيه ‎favored ‎4-31G (4 kcal/mol) ‎ 

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۳۹ 1 +(CUQ)O — راد 3 ‎@O OW‏ 1 OHaxial DOH oni (rans) 

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سل اما ۵7 < ماك 5 vel ow Best 0.7 kealmol ‘is-avetate srans-acetate 3.8. Approximate energy diagram for acetylation of cis- and trans-4-t-butyleyclohexanol. Cipro) even erence 

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وم سوه banaei sits سم ‎4-s-butyleyclohexanone‏ and irans-4-1- Fig. 3.9. Approximate energy diagram for oxidation of ci butyleyclohexanol Advanced Organic Chemistry (Chapter 3) 

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اف 0 Reo, ۱ oots — Ve "0 OfAVD) pyrowese uvetul OdVI) Onxidatiod POCHAUOOCG O-hetvester 

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وس اسواسوسصت۱ظ) 

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9 Me Cle 0۷۵ + ا ل + 0 جل و9 + 5 ‎“Ne es‏ 20%~ 20%~ 60%~ ی ‎>a +a f\ a‏ -0 + 2ه ‎~45% ~41% ~6% ‎4 a ‎ ‎stable up to 100°C ‎ ‎ ‎ 

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Ea (trans-cis) =17 kcal/mol AH* (ans.cis) =-20 kcal/mol frows-Oypcbhexeve: ot isvlated سوه نت معا ادص ‎9-S@": SO kedl/cool‏ bicyclo[2.2. 1}hept-1-ene (transitory existance) Pe utes even keratin acura) 

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000 < © < م < 0 < 0< 6 Q@ukhuta's Rule Por Ray Closure: u) Ring size b) Wybridizeiva oP the corboo ot the reuriiva ‏.عمست‎ ‎v) Phe rebiiveship oP the reurtioy booed to the ‏يح مت‎ Mesa une) ۱ 

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377) سمل ‎Coeds‏ رمق ‎sp sp?‏ و ‎Ring sp sp?‏ ‎Size | (dig) | (trig) | (tet) | (dig) | (trig)‏ ‎Pay Pay Pay oho‏ معا 9 ‎Pov Poy Poy way‏ معا نی ‎Pav Pov Poy Pov uo‏ 6 ‎Pay Pav Pay Pay Pav‏ 9 ‎Pav Pov Pav Pov Pay‏ 18 even kerk Acuna) ۱ 

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cancion ie 5 [= OW "۷ 0 cold ‏کت موم‎ 5" ‏رس‎ 0 0 وم جل كتمص 100۱۵ و 

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3.9. ۲0۳5۱۵۲۵1 2۳0 5۲6۲۵0 5 ina, Effects ۱ ۴ Cyclohexanone is reduced by NaBH, 23 times faster than cyclepentanone (sp? sp). 7 Ww (ko + ‘Dy 7 oe more favored as aE Ory [ ‏مر‎ ak 9 [ less favored General Rule: Converting of sp? atom in 5- membered ring to sp? increases the torsional strain because of the increase in the number of Pare 

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equatorial attack (favored for amall nuclephiles) (favored for bulky nuclephiles) 

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Felkin's Rule Ou Or Dediuve. Saal Dediuss Soot 9 ® Ou ® barge Large even kerk Acuna) ۱۳ 

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Cram's Rule OW ار ‎swaull‏ تكن ال جب اوح ‎Jess hindered‏ ‎side‏ horqe es 5 601 0 ‏تن‎ ۳ ۱ of R major minor 

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Norbomene Systems 0 major سب OW minor major 

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Study & Description of Organic Reaction Mechanism ۷ a =e AGYIET AG* =AH*- TAS* 

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4.1 Thermodynamic Data - AH=¥ bonenergiegnei- 5, bonenergiesen 0۷20 ‏خوالا6‎ Ne —e CUCACACe bouds Prved : CCL GAP keulloolbouds bokeo ? ‏بلكملك‎ 188 keul/eool CO _ Ce ‏اسلاسط‎ 9 O=O _(dde ‏اسس/امسیا‎ | 9799 ‏اساسا‎ 6808 keulkool ML= -GrQ0- (- RAG - - ‏ادد | اماه قت‎ AWS OS > exwikereic ‏سوه‎ ‎A> O==> eadothernic reaction Chapter 4) tren keri 

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0 89 100,۱۶2 2 7 :لول لو = AH ‏الات‎ 21112 Dy ALU rents AG = ۸۵ products" 2 ۸۵ ‏همع‎ ۸) > ‏له02-2‎ reuctivd AG > ‏کت(‎ vwou-spoutuevus reuvtivd Perr he rar acne) ۱ 

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مهن 0200 svdeswic ‏:عوشمه؟)‎ )( process in whick the ‏امین‎ oF Porwdl bouds oP ‏.الكوأعصصت امد ها ور موی‎ Uren hernias acta ae) ۱ 

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4.2 Kinetic Data جحهاممم جما خا ۱۹(۹۱ حاص لصم جما خات ججح هص مم08 (© () Gpevieropy ©) Cocduriowetry (iosic spevier) 9( Potarieetry (chirdl spevies) Qeuwivd Order: Is roe kw, cock poovediroica kos ‏او من‎ that is the OROGER vf the reactive wi respect to thot ‏.لمتكم بكمب‎ Uren hernias acta ae) ۱۳ 

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a (®) «۲۰۱۶ 2 0 CLO + ‏و0‎ === C1 + GOO rate = 0/۵ "our ‏حس با‎ 71 "لو (مهاتت)] / د ‎rate‏ 

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Dhe expressia Por the rae oP cay ote step ۰ ‏مت و‎ ‏وا و مر رنه تا‎ Por the cooreotcoicd oP pack reuvitny spevies. Step: oe = [AIBI- 2 [Cl , 10 stee: “PIs tc) , 11۳ 1۳ Step: ‏لا‎ 0) Uren hernias acta) ۱۳ 

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Gteady Gtate @pproxtcatios ‏ليام فد‎ Aa Kq 0 Kg + حفگ 0 + 0 6 + 5 + ‏ل‎ 1 ) + 6 PC is ‏اند مت تحص جا ,وعاصومد صاتاوداكى ,جمشعه ه‎ cever be very ‏ها‎ Tt west theo be poosuved ot a rote thot closely ‏انحا هم موه‎ the rote ot whiok it is Porwed. Oder these vowdiives, it is void pproxwoivd to set the rote oP Porwoiva ‏خام‎ C equal to its rate of desinuniiva. 

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ka 6 + © 8 4 ke C+@O—“> ۵+ © + © + OD —se. 62 + 4 TCI ‏ب‎ (AMBI- 0 ‏لعل‎ 7 {CII ‏و ااه‎ Mg 7 [ANB] =0 [C]+0 ‏[مالعا,‎ ‎_ 0 ANB] 0 7 ‏سوه‎ 0 ۱ ۱۳ 

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NY © ۱ ۳۳ rate= ,[C][D] 0 ‏سرت‎ ‎rate-J IAI) py 7 ADI+0 ‏ب‎ ‎i 2 {A][B][D if 0 [D]>>7_,=> rate-J ee =) [ANB] if 7 ‏در ا>>(طار‎ rate-/ 4 AAIBID] 0 @uck Uren hernias acta ae) ۱۳ 

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Uren hernias acta ae) ۱۳ 

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Oevkuvisw @: 0) 01000 WW ۵۵ 9 Rast ae ‏سره‎ 

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۲۵16 ,[H, ONO,][Benzer} [H2ONQ] poo uot be direviy weosured. ‎Tz ONGI 01 0‏ 02101812 ياك 21 ير ‎[HONG 0 _[NQ]‏ اد موه اه ‎rate‏ ‎[HONOP‏ ‎rate=J ING] [Benzer = ‎Uren hernias acta ae) ۱۳ 

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Fast ka 2 8 00 + 16200 عد 0م61 4 slow ح تک و600 e © WO + ‏وم‎ 00 

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rate-J [H,ONO,] eh © [H2ONOQ,) can oot be dire wecsured. 0, JH,ONOJING] _ p45 80) =/1HONGE a, [HONOP 2 17 01 ‏ل ا ار سور‎ 1107 7 ]510[ rate-J oa Uren hernias acta ae) ۱۳ 

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Devkusisw 0: Fast kg © 8 9۱000 ‏مب + وه + و00‎ 4 و0 ‎Fast‏ 9 ee + 0 ‏حلتب‎ 2 (1) 00 00 ka 1 ‏جح‎ + 17 qd) 

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1۵6-0 .]1[ ۲ 12 11 11 _4 .LNO2][Benzerk “4.2 [NO»][Benzerle ‏و1‎ [NO»] pen wt be dreviy weusured. 2 _ ۱۵۷90 | ae SS 5 NC = eee a, [HONG? [N02] 7 ۲2۷۹1], 92260 آر ۲ 0 یلار لا 262678۲ ۲ 1 یار اب if [H,O|>>[Benzenerate=1 ‏يه‎ 01 001 Uren hernias acta ae) ۱۳ [= rate=l , 

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MechanisnB: rate= [HONQ? obs Tata] [NQ] Orkney ® is zero order ia the reuctodt beazeur. It is true it severd ‏مت که‎ soveus 2 MechanismA: rate=l 7 eee Nee [NQ] [BenzetdIONG? سر ا-۳۵۵ :60671516 1۳,0[ 14 ‎these wevkudisws‏ ركجتالك ۲۳۳۲ ‎wer‏ رن ‎Te‏ اون 

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NZ Trnrstiod Grate Nhevry 2۳۳ اسشت مه تاه منت با صامسه: 9 تیه عمط 9) لو اوه مه اه ‎vowplex that yoes vo to product‏ Ratef activatatbmpledecomposin =“ h K: Trocswissive ovePRiciedt (usudly takes t7 be (1) ‏:عل‎ ®vlzween's poustact T: @bsoktte texppercture i: Plowk's ‏سس‎ ‎at room tempera Ratef activatesbmpledecompomn=6x1 0’s '(roontempera Uren hernias acta ae) ۱۳ 

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_ Ratef reaction” [Activatedomple} OP the uctiveted powplex is pousidered to be ia equilbrives Wits its Dowpouent: »_ ITS] ۰ K = [TS]=K’AIB TAI] (T.S]=KTAIB] Cree PuErp DP untivativd: AG* =- RTInK*> K* =e *0/* Uren hernias acta ae) ۱۳ 

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AWA 20۳ ۳52۶ reaction [TS], [T.S]=K’*[A][B], K* =e4°/*" Ratef reaction ‏مارم" عدن‎ :ترجاه مه نود Rate=/ , [A][B] Pre wuaroitude ve AB* wil be the Rovio, thot ‏جع‎ the ‏عل خان عل اموي‎ ot cay qived tewperdure. Uren hernias acta ae) ۱۳ 

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Zi cosep actions Uren he ran mune ۱۳ 

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:اه رفه) ۴و ‎=a ete ee AG -AH* oe TAS*‏ 7 7 ‎IRT) (SIR)‏ ای يد ,0 ۷ 3 Kk ‏و‎ ‎2-0 9۹ ۲ C= AS*/R T (e ) 7 (er) . = inl = an +C T RT ® pb oF ba (KID) us. (WD) ts theo straight koe, ad ts slope ‏جا‎ (-AW*/R). Uren hernias acta ۱۳ 

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كوو + = ‎AS* ag‏ مب( )۳/۳ ی) - KET @vivaticd Coen ond @rrkedius Equation: 7, =Ae F/RT 1۳0 , ‏موا+ گت‎ RT ® pbt of ta (ky) ve. (W/T) ‏جز‎ then ‏نت‎ ine, vad ts slope is (E/R). Cor reuntives ‏مشاه وا‎ of coustrat pressure, AW? ord Bare netted by: E=AH+PAV ,PAV=nRI n=1 . E, =AH*+RT 

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Cuz Prose: AW = dGSkoul/eool ‏اساسا - قل‎ Decomposition of 1,1'-Azobutane @-0=0-40 —— Gi + ‏وه‎ Gaz Prove: AW = G2 ‏اسااس‎ ‎AG = 9. koul/ewol 

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)٩عمشمع‎ whick ‏لصحام موی‎ species exhibit ceyuive EOTROPI1EG vP ‏اوه ون مره‎ ‎cu‏ .۶-۵ ۸۵۴ :اب٩60۵‏ 0096 ۰ انیب ‎oP‏ جنورباصراد8) ‎Rewvd: Becase oP its pol choruter, he 1.6. requires ‏ه‎ ‎reer ocderiay of solved crlerules thac ‏اوه ع‎ ‎Dke eothapy ond eateopy oP ‏متشه‎ rePlect the respouse oP the ‏ورد رفس‎ os 0 whole to Porsvotiva oF the uniivated moxwplex. ‎Uren hernias acta ae) ۱ 

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4.3 Substituents Effects and Linear Free- a ,. £&nergy Relationships Weaowet Cquaicd netotes rote ond equilibria Por woop ‏هو‎ oP lo i vs. lo x is Linea ۷ ae Ay: rete vousteat Por the hydeolesis oP ethyl bewzvate. i: rete poasteat Por the kydeolsis oP substituted eth ‏امعم‎ ‏ام موه سول له تیک‎ beazvic avid. 

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log k/ko -08 -04 0 0.4 0.8 12 log 6 Fig. 4.2. Correlation of acid dissociation constants of benzoic acids with rates of alkaline hydrolysis of ethyl benzoates. [From L. P. Hammett, ‏ل‎ Am. Chem. Soc 59:96 (1937).] Pern hea mcrae renee 

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wy loge =log => mlogK-logK) =(logk-logk) ‏وام يام ود‎ AG G =-2.3RTI logk=——— ogk = ‏و109‎ - ۸0 , ۸6, ۱ AG" | AG? 23۳1 2381| 232۳ ‎AG* + AG*‏ -= (,۸0 +۸۵ -0ط ‎MAAG =- AAG*‏ ‎Dke choage io the Pree coer oP ‏ترا متشه‎ oP ethyl beczvote ‏مه وه‎ oP oo sees oP substtuect yroups is directly proporiiccal to the phooge io the Pree eoerqy of iocizaion thot is coused by the suwe series ve subsituccs va becavic avid. ‎venir h eras acta ae) ۱۳ 

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—! rewntivd poostaat (slope) O! substiuect castact Pp und 0 oe dePiced by seleviv oP he rePerewe rewiou. the ivcizaiva oP substituted beazvic wide: p = 1 0 votes coo theo be deterwoiced Por u series vP substituect ovups by weorurewed oP the utd dssoctaicd coostat oP tke substituted ‏مج‎ ‏ان‎ ‎۵ ‏لصو ع ما موی عون‎ Por diPPencdt reuctious. 

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The 0 volutes Por ‏وان بو‎ nePlevts the ioferactioa The p vote rehect the veusiivipy cP the portiitar reunion to substituect ePPevts. P > 0 reuniivg kos oiowic ‏لها‎ ۵ > 0 reuniivd kos cotivcic ‏لصا‎ Uren hernias acta ae) ۱۳ 

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0.12 0.42 3 015 0.08 or 0.60 0.27 -0.04 0.65 042 047 0.82 0.74 073 0.99 1.05 1,23 0.08 0.74 Table 4.5. Substituent Constants” 06 0.18 =13 015 -26 02 —0.30 ~0.07 0.92 0.78 031 or 00 031 047 -0 0.26 0.15 0.44 044 0.24 0.70 0.14 0.13 15 0 8 0.73 0.12 0.14 O81 0.05 0.53 0.96 0.07 om 014 0.39 036 0.09 037 0.09 035 0.35 0.37 0.62 0.1 0.08 0.34 0 013 0.64 0.10 0.06 0.71 0.05 0.46 0.99 0.04 Substituent group Acetamido CH,CONH Acetoxy CH,CO, Acetyl 0 Amine NH, Bromo Br 1-Butyt (CH),C Carbomethoxy CHOC Carboxy HOC Chioro a Cyano CN Ethoxy CHO Ethyt Gy Fluoro F Hydrogen 1" Hydroxy OK Methanesulforyl CH,SO, Methoxy CHO Methyl cH, Nitro NO, Phenyl ‏باب‎ ‎Trifluoromethyl CFs ‘Teimethylammonio—— (CH,),N* Trimethylsily! (CH, Si a. Values of a,,,¢,,0°7 anda” from O. Exner, in Correlation Analysis io Chemestry, N.B. Chapman and J Shorter, eds, Plenum Brownlee, VO. Lopez, and R. W. Tutt, 166 (1979). Values of @,, and c, shown in bokifice type are regarded as particularly reliable. Press. New York. 1978. Chapter 10. Values of ¢, and ‏لج‎ from J, Bromilow. R. T. Org. Chem, 44: 

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۱ ۱۳ 

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‎ere rere‏ بای اه رس با بت تج ‎Gfevt‏ هه همعط (ه @ ۱ 9 ۱ و ۱ ‎Ole Qe 1 f‏ 0 1 4 ‎0 ‎0-0 ‎ ‎Uren kar (Chapter 4) 

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v) Seductive Get vy oy 80° 58 ۵۵ 88" ‘| 8 4 x Favored ‏سود‎ woRavored 

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AWA ZAK ‎d: The pK, value of p-chlorobenzoic‏ سنج ‎acid is 3.98; that of benzoic acid is 4.19.‏ ‎calculate o for p-Cl.‏ ‎K,, ‎p=l=> 6 ‏بک109 - می109< نت‎ ‎o =- logk,,- (- logK,.) = o=-pK,,-¢ re ‎o =4.19 3.98=0.21 ‎Uren hernias acta ae) ۱۳ 

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NY ‏حامج‎ ©: Wf the p value for alkaline saponification of methyl esters of substituted benzoic acids is 2.38, and the rate constant for saponification of methyl benzoate under the same condition is 2 x 10- 4 M's", calculate the rate constant for ‏و امنهر رامیت‎ Fano, =49 , k, =2x10*M's? HT Kno, =98x10*M's! Uren hernias acta ae) ۱۳ 

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UG 9: The p value for solvolysis substituted benzyl chlorides is -1.31, and the o values for p-NO, and p-Br substituents are 0.81 and 0.26 _ respectively. icine how much faster p-Br-benzyl fone lopide will soe ge og Nae ee 9 1.310 ergy] Chloride. a logk;, =logk,,,, + 0.34 logk,, =logk, no, +1.06 logk,5,- logk, jo, =0.72 k k log! 0/2 ‏5ك‎ 222-598 ‘P-NO; ‘NO, Uren hernias acta ae) ۱۳ 

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‎ae‏ اک ‎series beonee, ot substitucct‏ و ره 4 ‎ee eee ee‏ ‎Ottexvpts to develop sets DP O udhes thot ‏ضام‎ tp woot extra YukwowrT suc eq: log =po+p(0)(0" - 0) ‎K . loge =p0+p(NO - o) ie ‏مور و‎ porcoweter ood reflects the extect oP the ‎Uren hernias acta ae) ۱۳ 

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‎CPR erts‏ لاج ”) لحجه عممسووظا) جاه ممسمموق) ‏7 ‏وه مرا لحو نی ‎R‏ ۳+۳ 7< و ‎U. Ow. Chew. Gov. OD, FICO (1980)‏ ‎Geporaiva pP Rescue od iocuctive (PP evts er or log = 6, + PRO; ‎i K P19 + PROR ‎0, vdhues Kave ber dePiced Prow studies ic dipkutic systews where 0 Tresor powpourd should be presec. ‎Og voles con thea be derived by the ‏تمه باه(‎ ‏جك + رود و‎ ‎0 ‏0سا( ند‎ ۱۳ era usa tase |) ۱۳ ‎ 

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wuliyaruweter vartacs. By. ‏موه‎ Porweiiva neurtiod oP ‏:وعلرواعلاممودجا‎ ‎Oowtiaear Woaxvet Plot: p = 9.5 Por elevinxereteusiog yvups ‏ی فا ما با و‎ eames 2 BOWUDIOVS + AO Il WFO + CUMMINS OW 0 Oo I Il Il BOWUMUOM 4g ‏س7‎ BONFOVIO |G tren pic 

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44 asic Mechanism Concept 4:4:1 Kinetic vs. Thermodynamic Control Fig. 4.4. Kinetic versus thermodynamic control. ۱ urine) 

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9 5 6 0 6 9 ‎ll 0 2‏ © م ۹ = === ولاك اد اتن و اتن حمر 1 ‎6 ۰( 4 90۰ ®p voosttertay the of kudroyeds! Gtroay ved stericdly hiedered base ued aprotic solved ‎(Ktoric Product (cartier 9) Oevek buse or protic solve: Phereodpannic Product (rut 0( ‎Perr he rar acne) ۱ 

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4.4.2 ۲۱۵۱۱۲۳۱۵۳۲5 ۳۵۶۷۵ eduidud step to reuciiod werhuisd?: Pow sites, ey, T.G. ond ‏هجو وی مه‎ powepuively duday o neuciva process wad koe veut) the suave ‏موه روج‎ their ioteroouwersion wil involve oly sol ‏مرو‎ DP wolerutar structure. application of Hammord’s post Peruri Uren he raat acta ae 

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:موه ) Ole POs + Bo QOvderaie 

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SZ ۳ complies: intermediote Fig. 4.6. Potential energy diagram for electrophilic aromatic substitution سس ‎st 3‏ 3 ne, Pern h erin acta renee 

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Gl + Bry CI + Br; 9 + Bry Ne ‏د‎ a ate energies in bromination of methoxybenzene, benzene, and nitrobenzene. Fig. 4.7. Transition 

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oe 4.4.3 The Curtin-Hammett Principle ‏ام هی‎ CodPorwativa Cquilbria va Ohewird Qeuctioa. Be product Py conforner ۴ from B product a A 8 from A ۰ = = Fig. 4.8. Effect of conformation on product distribution. Uren he raster acta ae 

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رم بٍ لها بل ا 0 [ظ] 1 © ‎=k[A]=k,K[B]‏ د ۳۳۵06 0105 تمده 01 عتهط ‎ ‎Rate of Formatiomf Product P, - 28 - =kJB] ‎dP/ dt_k,K1B]_k Ke 02/06 KIB] k, @vvordicy to T.G. MRevry ond P.E. Diagrac:? ‎Product Ratio = ‎ ‎ ‎ ‎Gite 0 , AG? /RT ‏,ی ( ۵6۵6 لیس 1 کج (2 "۵0ج لفاك ‎k‏ ‎r h ky ‏۲و‎ ‎Urner hernias acta ۱۳ 

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,۵65/۳ 76 عاها » Product Ratio = a k, (kT faye “9/7 Product Ratio =e& 40*86>*a6-) @rcordiagy t7 the PC. Dircra: - ۸0 +۵0 +AG, =GF - GF Dke roiz oP product Porwed Prow cooPorwuiocd isowers is vl detercviced by the cocPer<oica populticd raic (AB,). Dke reaction wo be proceed through ‏موه وه هن‎ ۱ it is the var whic provides access to the nwesteueryp T.G. event heraaat ir acta ۱۳ 

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4.5 ۱50۲0۳۴0 Effects Sy ۳۳ 000 25 52 5-5 1 5 5 1 DP the substrate, but it kos oo ‏صمر جما جم اموطلتج للستخخصص بلاصك‎ ot sca 1 5 ۱-5 ‏خم‎ ‎2۳/۳ Peruri (4 عم غمهطء) رمخ ۱ 

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۲/2 9 : ‏اه ها م۳۷‎ C-W ®ord is betag broke io the rote-detercviniay step. (۰0 1-4677 /بوز 0۵ + ما00 حت 8 + وال6۲ oO 9 9 Cee + 0 ‏ی‎ CO) + (gs — Ky/ky=4.0(191°C) Perot renee 

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52 < 0.۳.5 : ‏اه عمسها ولو‎ C-W ocd is unt dinevily iqvolved ia the ۰ C-W ocd is tiqhteciag or lposeciagy ut the ۰ ky /ko > & ‏سوه‎ ky /ko © ‏هه‎ Uren hernias acta ae) ۱۳ 

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ky /ko > & ‏وت‎ ‎Oko to Oved Gireagts uu) chooge fo hybridization b) chooge to the exteot ‏زوم ان‎ ‎vP O-W boot. Phe‏ توا دكا بوص صا : کوب کرو اا ‎ba oe Che iy Bs Fe‏ 1 ‎3 ‏مص مور رین ‎oO ‎oo Kiy/ ky =1.30 (25 °C) 0 ‎ ‎ ‎ ‎GEE ‎ ‎Perham cutie) ۱۳ 

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Attn ky /ko > )] Iwerse “| ‏نو موی از كاوج مص‎ the neuctiod pester. ‎Oibraiod vP O-W bowed is restriciiag. he‏ : کوب کرو ‎O-W is yreuter thoa that Por‏ و وان ‎oP the‏ رشاو .لحمطا 0۵-0 ‎oO ‎1 ‎usok pro + ۰0 ‏)مه حصي‎ nor ga/ kp =0.73 (25 °C) oO ‏مح‎ ‎ ‎۱ ۱ 

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4.8 Catalysis by Acids and Bases steps ia 0 reuriivd wevkudisw by providey a ‏موی‎ pus Rovio 0 lower ‏اروت‎ ۰ TrawPer oP a Prowa Uren hernias acta ae) ۱۳ 

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| ROR + Ow ——~ OR —— Pvdurt Oo il ۷ I ‏وال‎ + © =— = GO=Cle + OW ۳ 1 @kO=Ole + (0 ‏ىلا30 ح‎ 

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Gperhc Bord Carpets: Dre neurtiod rote is iodepeodeut ‏خام‎ ‏مس موی جما چا ی تسه ام تفای سا‎ dowrs presed ica svhutiod. tis iodepeodednt oP the poaedroicd und spevitic structure DP the vorivus protoa doors preseu iv svlutioc. De ‏موی‎ rote would be o Pucotioa oP the pW. Thre ‏عون‎ expressioa Por way suck ‏یط نید توح‎ o ters Por ‏.ماك كالسا كج جوم حصا وج وساعروا‎ OPPereat buPPer systewws wits ‏لام وی‎ voles show idecticd neartiog ۰ Uren hernias acta ae) ۱۳ 

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Specific acid Catalysis با ۷ حك ۷ + 6 CL +o a ec = iy ke rate-K[BH ][C], [BH']=K,{B][H"] 1 ۱۳ رو [ 1۲][ظ] یک ۲۵6-1 ۳ Tracer actin ae) 

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Senne! Dke rewiiog roe is oPPevt by the : ‏مه اه‎ oF prota doors preseut it sohuiize. ‎eee‏ یا ‎protva dowrs presed ia svhutiod.‏ عون وا ‎Dre ‏موی‎ rote would oot be o Puootica oP the pI. ‎Tre hieeic expression Por way suck reuriiod wil ioclide terwos Por euck oP the potecidl prota doors tho wit us ‏.ادن ادا‎ ‎@uPer systews with dPPenedt coovecteatios (haviery ‏انح‎ ‎Uren hernias acta ae) ۱۳ 

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General acid Catalysis R + ۵۸ ‏ملع‎ + © 9 + ۳ sipw Rw + 00 oduct + WD 9 rate-k[RH ][A’], [RH JIA’ ]=K,{HAIIR] rate: K,,4{HAIR] =k,,{ HAIR] reverts Tracer actin ae) 

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MW ‏عنم‎ : Curnpsts baw: ‏نو‎ betwees the PR etivecess oP ‏مدن اووس‎ motels aed avidipy of ot prota dowr. log K.=a log K,+b ‎Ov. Okew. Gar. 08, Fd9 (1970)‏ .ل ‎Requrewed: Direct proporiivoaiiy ‏خام‎ A@* Por the votaiir step Por a series oP wide ty AG* desociciod oP sue series of ‏له‎ ‎۵ : @Croporiivcdiy coustodt skowiey the seusiiviiy ve the ‏رل‎ ‎troasPer step to that oP ‏متسود‎ oP uid, ood coo be used us 

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«مرب + [ ۲ 4 x 3 gE gg Fig 4.10, Brons ther (Adapt om ity] 

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Ooty tr Coweurued ode 0! H, =ogh, _[BH'ly,,,. A= ‏و115۳‎ Uren hernias acta ae) ۱ 

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Table 4.8. Hy as a Function of Composition of Aqueous Sulfuric Acid* %Hy SO, Hy %H, SO, Hy 5 0.24 55 3.91 10 0.31 60 4.46 15 0.66 65 5.04 20 1.01 70 5.80 25 1.37 75 6.56 30 1.72 80 7.34 35 2.06 85 8.14 40 2.41 90 8.92 45 2.85 95 9.85 50 3.38 98 10.41 a. From J. J. Jorgenson and D. R. Hartter, J. Am. Chem. Soc. 85:878 (1963). 

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4.9 Lewis Acid Catalys 0 o* Ose 0 poe o* = aw ۱ ‏مس‎ se © R o* o* ۱ NN o ١ Z ۱ ‏بو و‎ 0 6 000 i R i 9 Sp oo ا 9 ,2 6 Advanced Organic Chemis 

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ow = 8 > ۳ ‏یلگ ن‎ oe 2 On 3 ‏وا حت‎ ad ad 6 0 0 ‏د‎ ‎6 es 00 ad ‏)سل‎ 3 a0 Nett hele ak ties 

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4.10 Solvent Effect Macroscopic Properties: Properties of bulk solvent Dielectric Constant: A good, but not the only one, indicator of the ability of the solvent to accommodate separation of charge. It is a function of permanent dipole of the molecule and its polarizibility. Y use: The ability of solvent to stabilize T.S. of tBuCl ionization: log Keoivent =Y ‏هروک‎ ‎The Y udtue rePlevts privvoniy the iveizaiiva power oF the solvent. Uren hernias acta ae) ۱۳ 

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Table 4.11. ۲ Values for Some Solvent Systems’ Ethanol—w: Methanol—wate Percent ethanol nt methano! 100 100 80 50 Acetic acid Formic acid 1-Buty! alcohol Acetone-wate 0 3.49 90% Dioxane-water ainberg and S, Winstein, J. Aan. 

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Curried Drwwe of Coben Prkxty BOD): Orb to he ۱ specinn oP oo rePereuse dye, becouse oP soled polarity. Table 4.12. E,(30), an Empirical Measure of Polarity, Compared with Dielectric Constant £ £,(30) 8 Water 78 Dimethylformamide 438 7 Trifluoreethanol Acetone 42.2 21 Methanol 327 Dichloromethane 41 89 80:20 Ethanol-water Chlorofom 39.1 48 Ethanol 24.5 Ethyl acetate 38.1 60 Acetic acid 61 Tetrahydrofuran 374 7.6 Isopropanal 199 Diethyl ether 34.6 43 Acetonitrile 38 Benzene 34.5 23 Nitromethane 46.3 36 Hexane 30.9 1.0 Dimethyl sulfoxide 450 47 a. Data from C. Reichardt, Angew Chem. Int. Ed. Engl, 18:98 (1979), Advanced Organic Chemistry (Chapter 4) Peron 

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Polar Aprotic Solvents: Increased nucleophilicity of many anions. e.g.: DMSO, DMF, DME ۰ Protic Solvents: Decreased nucleophilicity of anions because of H-bonding. e.g.: ELOH, MeOH, H,0.... Uren hernias acta ae) ۱ 

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eereusiacy the Ouctevphilivity by hose trowPer Cutest ‏یمه‎ 1 ‘a ‎CO ©‏ ا م4مسسم6ه <4-مسصجك |) ‎ion cosy ‏لكل ك)‎ © 23 cx 7 ‏روالد ‎Aoroun-O‏ ‎ ‎Peruri ‎Perr he rar acne) 

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5م 6 1 i ‎UP—O-O0 lg —> Product‏ = وولليين + بر ‎sow‏ ‎(Rae OOCOsvaer (Gee ee > CO Wace (re oe) ‎Uuausition state ‎ ‎ ‎UO kel ‎ ‎AH of transfer of reactants = |44.0 keal/ml ‎dimethyl! sulloxide-water‏ لان امعطم ‎ ‎Fig, 4.14, Reactant and transition-state solvation in the reaction of cthyl acetate with hydroxide ion. [From P. Haberfield, J. Friedman, and M. F Pinkson, J. Am. Chem. Soc. 94:71 (1972),] ‎Prk racic acne) renee 

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441 Structure Effect in The Gas Phase Table 4.13. Comparison of Substituent Contributions to Phenol Ionization in the Gas Phase and Solution” Substituent increment in keal/mol” x ‏مب‎ Mp, Guo AH m-CH, +04 +04 +018 +0.02 p-CHy +13 $13 +042 +0.02 mC) 9 9 -12 —03 p-Cl 6.6 -6.6 -07 ~0.2 p-NO, —25.8 —25.8 8 8 a. Datu are trom T. B. McMahon and P. Kebarie, £ Am. Chem. Soc. 9922222 (1977). b, The tabulated increments give the change in AG and AH resulting from replacement of hydrogen by the substituent specified. Advanced Organic Chemistry (Chapter 4) Peoria 

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We ye < aS [AG ]has phase7> [AG 556 [A ‏جنر وگ‎ [A Sloas Pphas¢ AG=AH- TAS = [AH gas prasc?> [AHI solutio vidity Order ict Gohutios: HBuOW < WO < GOW < OeOW rvicity Order ict Gos-Pkase: HBVOW > GOW> DeOW >> WO Uren hernias acta ae) ۱۳ 

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4.12 Stereo Chemistry Aerts ۱ ۱ Ni 3 7 iC 060 ‏ا احبر‎ wa 3 N O + ‏جد وه‎ 4 Gr 4 1 000 00011, + ‏كمي جد به‎ 2 >» ‏موم‎ AL HOOC A @ Perr he rar acne) ۱۳ 

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Chapter 5 Atti 

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5.4:The Limiting Case-Substitution by the ۱۵۳۱۲2811010 )5,,( ‏»ع‎ 1 

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nergy Poter Reaction coordinate Fig. 5.1, Potential energy diagram for nucleophilic substitution by the ionization (Sq 1) mechanism 

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5.2 The Limiting Case-Substitution by the i¢Direct (S,?) Mechanism aM _. 47) Rx | rate=- ——_ dt سس سا ف ی 

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Potential eneroy Reaction coordinate Fig, 5.2. Potential energy diagram for nucleophilic substitution by the direct displacement (Sy2) mechanism. Pre WOOO a the T.G. is 1 ia choravter, therefore T.G. ‏توص‎ ‎should be lowered by ‏ی موه‎ odecedt substtuccts. 

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QMO Qescripioa CSSD ندا سا لد ها وی اس 

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5.3 Detailed Mechanistic Description and »,,¢orderline Mechanisms Otesteta: Oru ept oP iva pairs Qtacktay the Duclephie or Golvect: ui Need ASML ۳ 

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eiodted aad Goled Toa Pairs: ‎uceivoe und water‏ 00% یر ‎Tous:‏ لح ‎9 ‎1 =23 Gide 9 ‎ 

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we ان مقر ‎oP cuclephile to the spstew )0 .062 0 )000(:‏ مس kf Ov Quvewization 

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sitepe Lebetay! (oerd bredkiog without cet substitution ‎se ١ :‏ 2 كلابب براوراعمصی بحخصحص ها هوجو وه مهو وم وا ‏ان اصوانی لو مود ور رز ‎ ‎ 

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ae هافر QOrwoestrutiag the too por returct Dre rote oP devreuse oF optical rotaive is qreuter thoc the rote oP product ۳ ‏سلادوو‎ مها مه ‎Gat GPRect: Oddiica oP sults ypicdly causes‏ سیم ۱ مه سا ‎uh‏ عن عنوررامربامد ‎the rete ve‏ ‎the‏ خام أحمصممه ‎ia dielectric‏ وحم ‎to the‏ صك) مه ا ‎wedi).‏ 

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( 8 11 1 1 (obi loo pairs wight ut voy be involved it ud povesses but uso ‏ماود و‎ 1 1 J exchibiticrcy ine sSlerevrhe wird ‏لجن‎ hictetic DRurupteristic oP the 17117171555. 

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intimate solvent- dissociated ion pair separated ions ion pair R-Y.X ic relationship between reactants, intermediate species, and cts in substitution proceeding through io 

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Relationship between stability and potential lifetime of carboe sm for substitution 

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5.4 Carbocations 0 Wert is ‏دبای ام بر ! عاطادمح"ا‎ ۱7۱2۲ tt spied is Deusibie Deb wUsSe DI Sivan. Gurdewes: (1) Liquid GO, ‏«مشامك‎ oP PK CCl is coeductiagy. 8) Pk,COIg hes ivaie bekovior. 

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id Rekaive Gtabiliy دانم سام قد [R*] =log—— + H, pK,, 0 [ROH = 1 ‏خی عا ۳اه مت نله) سل‎ Por ‏شاه نله‎ = WW 

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‎Some Carbocations"‏ ۵۲ 0۸ ۵۲ با 5.۱ عاط ‎Carbocation ۳‏ ‎Triarylmethyl cations‏ ‎Triphenyimethyl 663‏ ‎Trimethyltriphenyimethyl 3.56‏ ”4 ,4.4 ‎4-Methoxytriphenylmethyl 3.40‏ ‎4.4'-Dimethoxytiphenylmetlyl 24‏ ‎-Trimethoxytrip! methyl +0.82‏ ,4 .'4.4 ‎4,4/.4”Trichlorotsiphenylmeth 74‏ ‎4-Nitrotripheaylmethy! 9.15‏ ‎4°-Teinitrotriphenylmethyl 62‏ ,4.4 ‎4"-Tri(dimethylaminoyriphenylmethyl $9.36‏ 4.4 ‎Sesquixanthydrul $9.05‏ ‎Diarylmethy! cations Dipheaylmethy! 4.4 -Dimethyldiphenylmethy 04 4.4’-Dimethoxydiphenylmethyl ‎’, 4.4’, 6, 6'-Hexamethyldiphenylmethy! 66 ‎4,4-Dichlorodiphenylmethy! 3.96 ‎ ‎ ‎ ‎Miscellaneous carbocation: ‎ ‎Benzyl 20 2-Phenyl-2-propyt 23 Tricyclopropylmethyl 23 Tropyliuin (eyeloheptatrienyl) +47 ‎Triphenyleyelopropenyt $3.1 78 Tricycloprapyleyclopropeny $9.7 ‎Trimethyleyelopropem ‎ 

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256 237 225 9۴ 233 220 ‘Table 5.2, Hydride Affinity of Some Carbocations Hydride affinity (kcal/mol) “HCH, * O- - 0 31a 27a 24۳ 230" 287 cH! CHCH,* (CH,),CH 6 سین 

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Crbilie Order oP Cwbovatces Based ‏من‎ Gobobss Rute: 9 << 1 < ‏تيراكن‎ Grobiizaiva oP Ouwbovaiow: 

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‎ePPevts = vP OY@OOO un POROYL‏ تال ‎۲۲7۶77 ‏ال‎ less than DO wethods predicted ‏,اه‎ ‎۷ ‏:مصاه) مسیون ‎ta-Cyclopropyl wethyt Caution > tr-pheol wethyl ratios ‎ 

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هم ‎Cg‏ اه هی 019 ری ‎Cg‏ ‏وب ‎Og‏ 

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Gtady oP Carbovaioes Qearraneweut OO Sperrvscepy fa supper onkd coeds (crac uid): COSW - GbR, - GO, Cowerbul ‏رتم‎ ability: Ove-Oucterphili Cuorboouives kwe Gp? hybridization 

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5.5 Nucleophilicity and Solvent ۲ Cake CPt on Owe eo ido: 0( ® kik Gobaica Coerepy oP The Ouctephie bwers he 6.6. ocd ‏كدج وما‎ the uniivoiogd ۰ ©) Gtrouger booed betwee curlevphiic ‏موه‎ ood corboo couse the stubitzativa oP the T.G. ood wall reduce the ocivotivd roe. 9) ©@ bulky curlephile wil be tess reartive theo sadler var bevouse oF cwwbouded repubsivas that develop ia the ۰ .اوه وهای ها راشای الا S) Colarzibhip: ke wore eusiy distorted the viow, the better its uclevphiliviy. ‏راودا‎ inoreuse wil ‏توت‎ suber ypieg dows it 

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QePerewe Rewitod Oethouw)sis ‏خام‎ De-1 Dyer =log ‏تازه وه رزو‎ Keon in MeOH, 25C 

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ic Constants of Various ‎of conjugate acid‏ يكار ‎ ‎89:1 ‎An. Chem So Am. Chem. Soe ‎ ‎ ‎‘Nucleophiles* ‎9.25 ‎474 ‎9.89 ‎157 ‎tee ‎58 ‎79 ‎10.70 ‎6 93 ‎ ‎10.7 ‎3.09 ‎98 5 107 ۱5 ‎Pearson and J. Songstad, J! Am Chem So ‎ ‎and 1. Songs ek and G. M. Whitesides ‎ ‎7, Nucleop! ‎ ‎Nucleophile ‎HOH ‎0 ‎F ‏بت‎ ‎(CHS ‎NH. ‎Ny ‎CHO ‎Br ‎0 ‎HO ‎NELOH ‏ابا‎ ‎(CHSCH,),N ‎CN ‎(CH.CH,),As ‎1 ‎Ho, ‎(CH,CH,),P ‎CHS ‏مدا ‎(CHa), 80 ‎a. Data from R. ‎(1967); R.-G. Pesnion, H. Sobel ‎90:319 (1998 ‎4p. ‎ ‎ ‎96:2826 (1 ‎ 

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ane era QOutlevphiiciy cd @usiciy Qelivaship The vorretativg is better iP the ottachicgy uve is the suave OW,O° > PkKO™ > OL ZCOO™ > OO5" T> Or < ‏إن‎ < 0: PKGeE > PKG" > ‏بات‎ 

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se ee Ovwept DkerePore, 0 svt ocivn should at os ou culevphile, yivicgy the substituics product, while ‏و مت لو و‎ wore likely to ubsirat o proton, «vier the ‏ارم ماه‎ Table 5.8. Hardness and Softness of Some Common Ions and Molecules Bases (nucleophiles) Acids (electrophiles) Soft: RSH, RS~, >, R,P 1,, Bry, RS—X, RSe—X, RCH, —X ~C=N, ~C=0* RCH=CHR Cul. Ag(). ۳۵۵ ۳۵۵۰ ۱۱1 benzene zerovalent metal complexes Borderline: = Br-, Ny>. ArNI, Cul}, Zn(lD, Sal) pytidine R:C*, RB Hard: HzO, HO. ROH, ROT. RCQ,- — H-X. H*, Lit, Nat, Kt ۳ 0۵ ۱ NH,, RNH> R,Si-X 

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ae دانم سام قد a- GPPevt tows whiok oe direviy booed to ‏موه مه‎ wi poe or wore weoshared purrs oP eleviroes ted to be stroayger curlevphies tho WOO’ > WO” ‏رن )کیبل‎ OW OW > OW, 0( 00.8. ‏شوه‎ cP the cucleophie by lear poirtooe pair ‏انح‎ ‎0( ‏ام وا را ۰۵۰ اه روص وه اه منساط)‎ 

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‎DeOW:‏ .وج ,جامد ‎order Is protic‏ متا نز زر ‏0< ع© < 1 ‎Ouclevphilicty order ‏ر .۳.۲ ,لاه ره ار وا‎ DOGO: ‎Ow 3 Ol‏ < ی ‎ ‎ ‎ 

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id 5.6 Leaving Group Effects GN eee Pee Ree hee cat crn comer ae Bobo ‏رت‎ DapUvily. 06000 << 00 ke order of reaniiviy oP the kode leavien wou (O-X bow): 7 >@r >Cl>>e Aoaeeasiony ke y by coor dicate 17 v Phe reuciivg is yreuly uceleraed fa uvidic wedia. 

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Table 5.10. Relative Solvolysis Rates of 1-Phenylethyl Esters and Halides*” Leaving group Kat CF,SO,> (triflate) 1.4 x 108 p-Nitrobenzenesulfonate 4.4 x 108 p-Toluenesulfonate 3.7 x 10° CH,SO, ‘ 3.0 x 10* 1 91 Br 14 CF;CO; 21 cl 1.0 F 9x 10°° p-Nitrobenzoate 5.5 x 10-® CH,CO,~ 1.4 x 10-6 a. Data from D. S. Noyce and J. A. Virgilio, J Org. Chem. 37:2643 (1972) b. In 80% aqueous ethanol at 

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ane Atos 5.7 Steric and Strain Effects on Substitution 4a privvary uk! substrates the reuniiva rote depreuse wih iaoreusicy Table 5.13. Rate Constants for Nucleophilic Substitution in Primary Alkyl Substrates“ 10° for RCH)X CH; CH;CH;— ‏ی ات‎ 99 64 15 0.00026 154 64 49 906 33: 67 0.044 0.018 0.0042 Reaction ‏لفاحم‎ ‎RCH,Br + LiCl, acetone 600 RCH,Br + Bu,P, acetone 26,000 RCH,Br + NaOCH, methanol 8140 0.082 RCH,OTs, acetic acid a. From M. Charton, J” Am. Chem, Sac. 97:3694 (1975), 

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مر ‎T.G., the‏ نش جه موه له تمه ووم ‎a the‏ ‎Pactor.‏ مه روا چا جوا ‎note‏ مات ‎vets: ‎ ‎ ‎ 

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ae هافر O-Gtrua (Bat-Girun) ta Wich Orawhked Gpetews Cucidte The Iotzdiva: :اج لطي % ‎١ OO‏ جاو رباصطمررا!” 

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Table 5.14. Relative Hydrolysis Rates of 2-Alkyl. adamantyl p-Nitrobenzoates’ cl CH,CH, (CH,);CCH, (CH,)5CH (CHs),C. a, From J. L. Fry, E, M. Engler, and R&R. Sehk 94:4628 (1972). b. Relative to ‏ام‎ 

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‎Substituent Effect on Reactivity‏ نت ‎0-Oxubsturct ePPet: Direst 6 ,,° reuriion proveeds wore eusier thea‏ ‎Go neantivg it O-kolo derivatives oP ketvoes, uklehydes, uids, esters,‏ ‎Table 5.15 o-Substituent Effects“‏ ‎X—-CH,Cl + I> + X—CH,1+ Cl ‎4 Relative rate 4 Relative rate 0 CH, CH,CH, — 1 Phe 3.2 x 104 ‏و۳۵۹0‎ - 025 N=c- 3x 10° 0 0 ‏لورت “10 »3.5 رت‎ ۱۳۵ 103 ‎a. Data from FG. Bordwell and W. T. Branner, Jr, 1 Am. Chem. Soc. 86:4545 (1964), ‎ ‎ ‎ ‎ ‎ 

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5.92 Stereo Chemistry of Nucleophilic Substitution zi, Reuctiod oP otovkols wit GOOL,: 

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locke! ‏اه مه (1) :ساد‎ OodPicpucaiiva ster Porwatod: Retectiog vod iwersioa is wore sicior. 

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Rea 05 9 999 کر "10 ‎k= QOx‏ (© 000) ©0004 1.6 دم ۹8 999 ۳۵999 مس مر اس رما 0000۵ 

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ار Chemistry 

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LES 1 ‏لمات‎ —> + 10 O 4 Lemme HOCKCHOUCIO 0 ites 0 0 ei) (®) ONOOUOW WCW Ne, ‏د‎ A 0 a. banaei 

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وج ‎oP eter‏ وا موسوم 

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7۲ @levirvd ve C=C Cortvipaiva Ovetolsis oP Oorboraeurs 

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‎Cleviroa ve O=C C@urtcipaivd‏ 0 جه مس ‎ ‎Det 4 Gubstituiod at O-? posiica oP Oorboraedes ‎ 

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7۲ @levirvd ve C=C Cortvipaiva (Porwolpsis ve ppolpped-O-eut ‏اه ارجا‎ 1 bh fy 5 Reteatiod ve oct Ratio 

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Gyohketc Ose vP 1 Cleviron vP C=O Pountvipaion Isis DE O-pyolopedt-O-eu eth tosphate: cet ۳ 7 3 3 re} 1 0 0 ١ 3 

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Crewe 1 Clevirod Porticizatiod (Phectucz Toa) B-pheS <proup ponicizatica Cr 

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svwpe ‏بماصل!‎ ده مر ۱ وه ول p=0.7 osiively charged T.G. Orvck substitucct ePPert 

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مر 5.11 Rearrangement of Carbocations : 6۱0۷ روك 1,6) و با 4,91 Oriviey Porve : Porwativa oP wore stable varbovutioa 3 ‏م‎ XY 1 5 

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5 GPPect oP Golvedt QOuclevphticiy va ‏خان بح‎ 101 ينا 

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il a. banaei 

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ار Chemistry 

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ae atest مهو )( ۱ ‏,وراه‎ 0 barge pot oP the reuriivd wost be vovurrieey DUDS. 9( Wa) werauwlevphiic super wid wedi, the volivw evectudly feadicgy to the wost stuble accessible iva. 

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ple wows 0,S-W- GRR: OpclowayHd-C tosylate 

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0 0 9 SG Oo (©) 3 00 200 را Gee Gee (ebsewed at -IGD°O) 0000 000 7 0 a. banaei 

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aytiide-bridge ion ta whick the bricetacy ‏وا‎ ts located to pestle ‏.ععمج مر و‎ 

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Cutbovuiod Qearake wed Puciitaiog via The Product ‏«اف مقر‎ Gtobitzaiva by a Puerto Crow وس و ۳ enn 

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۳ ما 0 انس معاد a oats Dae) 

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5.12. The Norbornyl Cation and Non-Classical int, Carbocations Optically Ovtve Exo Orosvlite = Exo Produ (dOO% revewizati) Optically Ovtve Gado © ‏جیار وم‎ > Bx Product (90% ravesizaivn) srk 

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3 3 6 5 7 9 

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W 33 ناوات موااو ار 5 01 مها ام وولو تما م9 انا ات ‎(place vPsywoiny) 5‏ Advanced Or 

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a ‎iva cod oer‏ ۱ لك ات ابو ‎Rupicty‏ یبوط ین را ‎chossicd ion us T.G. ‎ 

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onclass bridged io classical ion 5.11. Contrasting potential energy diagrams for stable and unstable bridged norborny! cation, (A) Bridged state for rearrangement between classical structures. (B) Bridged sa transition ent of one classical struc (C) Bridged nonclassical ion is the only stab jon is an intermediate in rearra the othe structure. 

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«اف مقر Wik ‏:عمد عمد حلص‎ Cowpuricry oe exv-wrborayt ‏ارو‎ wit ppolopentl bros hate ued ut wits ppolokexyl brosplate (PrePereue Por exv (۰ سس ۱ 

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‎be ea pce eee‏ ا اه 2 ل 2 م1 ‎i uquepus Dipxudce‏ ‎ 

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مقر ‎Tow:‏ :)۲ حصمطزر۳) ‏ل (6 

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Chapter 6 

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Introduction ®Q) ۷ ‏حت‎ ۲ + ) + ۱ x ‏وت‎ Dee 2 ‏یه ۱۷۳ رد‎ oe 2 eC Y Advanced Organic Chemistry (Chapter 6) a. banaei 

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bin © ©, ‏کسیر ال ور حب يوسو + د‎ e 6 Bimolecular Electrophilic Addition (Ad,2) Ye ¥ ©) ‏بو‎ + 77 ۳ Soak =~ Sa + 6-4 ved Termolecular Electrophilic Addition (Ad_3) Advanced Organic Chemistry (Chapter 6) a. banaei 

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63 Addition of Hydrogen Halides to Alkenes Qewoselevive Rewtod! Oupewetiod dkhew yours a predowiccase oP poe oP the two possible uddiica products. ‎FRONWO AY + RONO NAC‏ ۲۲ + ماال‌حاال 0 1 ره زد اه )رز صاصج من عظ) ‎Advanced Organic Chemistry (Chapter 6) a. banaei ‎ 

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لو ‎Ove pods if‏ ی( سس ج) ‎X-Y —» 600۵۲ (Caly Poduct)‏ + انع اكوم 1 ‎Reyivspevify Reurtivg‏ Ockdica oP Wydeoged Wakes to Olkeces QDuarkowrihoPP’s Rute 9 ‏کر‎ x RO=CUR ‏یت‎ 50 —— ROCTAR | KX wore Favorable Advanced Organic Chemistry (Chapter 6) a. banaei 

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مر @xkhtica oP WCH or Wr to Chews: ۲۵۲-۵ Sone! « ra s AX iw ۳ oh ۳ ‏تور‎ + We ‏میم‎ + aK x Advanced Organic Chemistry (Chapter 6) a. banaei 

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Ve sterevokewstiry 0۴ ‏مللی‎ oP hydrogen buldes to wooded dhrues t& predowtadriy ۰ Advanced Organic Chemistry (Chapter 6) a. banaei 

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‎newsios wan be wodPted by tewperdure wad‏ موجه ‎a. banaei ‎le ‎Ai ‎1 ‎Vert) ‎watt addition product ‎a2 ‎6۱0۲۷ ‎1 ‎“Me ‎۱ ‎product ‎90 ‎oe ‏۰ رو ‎Ole ‎+ WO) Mg 0۵ ‎+ Wo Cle ‎Advanced Organic Chemistry (Chapter 6) 

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bin Out sterevckewstry von be exploited by ‏یب و ون و‎ the thew tera stool) wih te proordoodicg WI aed wily the kolide source. ناك “ىم رم ‎wa‏ Advanced Organic Chemistry (Chapter 6) a. banaei Pw 

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)0 ‏ام اي‎ varsios ia the stereockewisiry to observed ‏بت‎ ‎ke, dubs bood cociucaied wil ‏ضحي و‎ thot oot sities ۰ ®rruse oP yeuer stubiliy oP the carboouivd (spevidhy ia ‏(مصتمىيومت صتعصصه‎ coUerted utack by kolde ion (Bd, O wevhovisw) is ot required ued Porwed io poir colopses ‏ما‎ ‎product Poster thao roteiva tokes phooe, the result wil be sya addiica. Dhe neuctivg is Pirst order it WOM. Advanced Organic Chemistry (Chapter 6) a. banaei 

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‎Goivedt tr Ductevphiic Golvects:‏ ارب متس( راون یمه ‎a 0۶‏ ‎222006 ‎oP kale su ( (ex, Deg @*X) iupreuses the vupture‏ منطل) ‎ioc.‏ ناه ‎porbooution iterwvediate by‏ خاص ‎Advanced Organic Chemistry (Chapter 6) ‎NO ‎(PkOWFC lg —— NOs ‎a. banaei 

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هس مه ما بت سرت ‎ee‏ ‎(Cl OCU‏ + مامح م0۳۵0 ‎ot‏ بل ‎eon‏ . ‎0۹۸ 229 ‎© ‎(CUQeCUCTFO Ng —> (CUQ CICS + 09 - ‏لاك‎ [7 ‏را © ب © ولیک (0۵) ا مایمن تمسماساموم ‎a‏ ‎fan (CAg CIs‏ ‎a‏ ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

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دسم( لادب و0 جا مطل) ۳ 00 ا + ‎C1OW-ONRCICND‏ عد هالا حرا ااا الاح ا وباك ۱ a a 2069 Boe 4, @dditioa Qoduct 0,9 Odditioa Qodurt ‎Obutadiedr: OigeOrckasisw‏ )و14 ‎ ‎۳ ‎5 9 ‏امس م سوه‎ Ye ‏حد امک‎ ٩020م‎ AD a ‏اب‎ aad @eazplic QE @dditiod Aoduct Qobilizatiog ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

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@dditiog oP Wr aad WO! to Oorborcece testi 0 0 ‏مر 0 دجم‎ way Oidge ba oy aim &, repped to the chloride iva. Advanced Organic Chemistry (Chapter 6) a. banaei 

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۹ ۹ 

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6.2- Acid Catalyzed ۳۱۷۲۵۲۱۵۳۱ 0 i. tkelated Addition Reactions ‎Ww © 1‏ سئب ۳0 که 020 ‎ ‎PROU=OWD ‎ ‎AD ‎Fast ‎ ‎ ‎ee + ۳۳۵2۵۵ OW ‎woreurted ‎() Geuerd uid catalysis 9( Golvest ieviope ePPevt (Buco! ۹ =o?) Rue ‏ترا‎ Crowson ‎Advanced Organic Chemistry (Chapter 6) a. banaei ‎ 

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@Ockdhicd oP Ducevphiic Golvecs: PP ect oP @oicliy Oleve-ucld vowplex with wedker ucids dion oP Or to vis~ or traws-O-bueue (Od, 9): ۳0 bin O41OURACIONs == O10 ‏م20‎ ۳۳۲ 1 ONLOWECIC Ng, ——> eae te ati Oddition J (sterevspecific) GOW Advanced Organic Chemistry (Chapter 6) a. banaei 

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bin @ddtica oF 00 fo i= or trow-O-buter (@d,2): 9 1 © ماک ۲۱۲) حتت 0 + وکساک oO oO 5 | ONICHA, + CrOI — ‏ال‎ ‎on Oddition Advanced Organic Chemistry (Chapter 6) a. banaei 

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6.3 Addition of Halogens ۱ ae bene meeh pourented? ©) IP there is u positively charged interwediuie, is to carboroiva oro ‏ممصا عنامت‎ “Ia? SEN 9 cs ‎is ® ۰‏ م ‎es‏ ۷6 = ,با( )چا ‎eo‏ 2“ ماه ‎۳ ‎ ‎peo carbeoulion ‎Cor Orowitiocs: Outi odditica is prePermed Por dheues that coo ot stublize 0 vorbovdion totercediaie. ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

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ارت کاب لم‌خی اه سا ها جسی مسا ح مللی ‎Gps‏ ۷-۲ 9 ( o rt So oe ‏و‎ O—C. = : .لوك 8) نو()) مس موز لل:97) تحص عام9) Crowe Gystews (ClviveRebwiny): Gtubiizciog cP the vorboraion oad loo par wevkacise (Spa Bddiioa). Crowe Gpstews (Clevver Ptractay): Orstubiizaiog oP the ‏له موم‎ bridged iva werhudisu (Buti Pdditizc). سس وه & ‎Oprese‏ Advanced Organic Chemistry (Chapter 6) a. banaei 

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‎oot‏ سوه و ,صاطادو امم یا ح وال تیان ‎oor bridging yup trod brow. Gyo additog ts siykiy prePerred Por chloricratioct. Cor wrrcouuysted dheurs, sterev ‏لت سوه‎ oddiiog is usury ‎observed Por botk ‏ال‎ ‎Gurdewes Por pyolic brooar ton! ODOR Gpectrvoscopy ‏اوه بو‎ ‎ ‎Devkacise study 

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A 1۳ AAH* from steric repulsions in 0000 transition state 4 ۷ AAH from steric repulsions in ground state 1۳9/5 Fig. 6.2. Enthalpy differences of starting alkenes and transition states in bromination. 

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Qheetic oP Orowicraiod atest rate-k[Alkene]f#]+ &[Alkene] ig? + k[Alkene]iB [Br] ‎ocd high coon oP (Br kieetic is poeudo-sepoed-‏ امس مب ‎order.‏ ‎rate- k[Alkene ][§][Br]‏ فصو ‎Goilurto the‏ 0۵ ‎Ze ۱‏ بد ‎No-ke se‏ يه 0و ۳ جم 3 ار ‎ena‏ ‎Dn os K+ @&‏ ‎Oo‏ ‎Advanced Organic Chemistry (Chapter 6) a. banaei‏ 

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‎rate-k[Alkene]bB]+ &[Alkene ]hB)‏ كت ‎ ‎ ‎ ‎Geoodorder terx? 6 9 Be ce is ‏سس خسف مر‎ ee cae & i ote Ou, chore trouser ‏دور‎ ‏رونت‎ ‎۳۵ ‏:ها لول‎ 6 0 ‏همه همه‎ ee 5 ‏كك‎ \ pee /e\ 1 ‏رس 0 ا > 0 ار‎ + ۵ a. banaei ‎Advanced Organic Chemistry (Chapter 6) ‎ 

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‎ONpricdiva? Overcy O°°-Order. Pirst-order ia bots‏ جن عطق ‎ud ©}‏ باه ‎ooneusiog the neuciice rote wih alkyl substituion. ‎ ‎ ‎ ‎Okew ORbrteratos: ‏سس‎ ‏0.04 وا ‎۱۱۳۹ 000 00 ‎Se eeu 6 06 ‏عمجف ©)- جزم‎ 69 0 ‎SO 95‏ ین )سونو ‎Se eee ‏ه66‎ SP 5026 000۵ 960 ‏۲واممد-9,5‎ 9-1 00 190000 ‎ ‎Advanced Organic Chemistry (Chapter 6) a. banaei ‎ ‎ ‎ ‎ ‎ ‎ ‎ ‎ ‎ ‎ 

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Ceopetive CQeawtows cP ‏لصا نا‎ in ‏وان‎ ua) boss oP Proton a Ro Je © p 07 086 or ‏رون(‎ —— pO + Ww ‏ی‎ 04 RO Cte (CtgO=Cte + Oe —, CiEOOhKO 829 0 ‏وه + تابون ره‎ ۷۵ 06 a Advanced Organic Chemistry (Chapter 6) a. banaei 

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bin b) Oly Oigratios Pe CID SCt-Cin + Cg tes ~di% ‏ها‎ ‎Pte ‎(Cig MCwRCIKCiige + ‏هت جح وله‎ 56 Ag Advanced Organic Chemistry (Chapter 6) a. banaei 

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luoricration C4, Byrorios wi ‏اه‎ te vilect ives ‏مب ده ماوت‎ ‏.عاص لصوم‎ ‏اه ط و( اه لت اامسسط9)‎ a) Xe, or viker elevirophitc ‏سس(‎ derivatives. ‏(ط‎ Wight) dhute Pot low texpperctune (sya uddiiog, too pair ohopsic). Gtereo chewicd ‏هلاه ماو له اجه‎ امه ع ما منم وال97 سمل .اه ‎oP excess‏ موم ۳ وا مره سوه عا مل؟) ‎Dhe uddiica is sterev speviticaly ctl.‏ Cota or ‏لطس الم‎ is involved. ‘Advanced Organic Chemistry (Chapter6) ‏مهو‎ 

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‎Counted Oieves‏ و فیدر ای ج تسا 00 مد الاح كحماسا ۱ ‎(C's‏ ‏69 99۵ ( الم نلک م:1) ( الم موننللم1,9) ‎0,-Oddticg ced coivair toterwedate wi Or, (Gtere speviivaly sya).‏ 8 8 سل تالصوو سوس 00 شك ان المسابم روس اتن ‎3 ‎0 0117 (Pg Devhaniow) wit ‏راتس )عم لاب‎ wef). ‎Os ‎AOGO—O= Ole —> BOUMOUMe ‎= Oe ۷ ‎Advanced Organic Chemistry (Chapter 6) a. banaei ‎ ‎Cle CWON=C Ne 

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6.4,Electrophilic Additions Involving Metal ~ lons Oxpwencurciod 9 ‏“عاك‎ | 1 ROW + ROUHFCIR —S ROLOCIRT W ١ OR Osc curlevphie is the solved, but cher cuclevphies co ‏موه‎ ict @evause vP steric ePPevis, reuciiva poo ut be uveleraied by dt substtucds a the ‏اه‎ Advanced Organic Chemistry (Chapter 6) a. banaei 

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bin ح م6020 0 ۲ لا دناه ف صصص ‎bridged‏ ‏9 Advanced Organic Chemistry (Chapter 6) a. banaei 

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‎Ww 1‏ ‎I he‏ ك5 عت كد جك تر ‎w+‏ ‎dydroyes Bidged ‏كماد‎ ‏واه ‎hos oo uoskored‏ لجی له لها عا مسسم ۳ ‎Dhe vorboodivs or hydeoged bridged ts clevinva ‏ول‎ aad rewive. ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

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© a oe ۳ a “at — ‏اس‎ — Gy se ‏كر‎ QL ani The positive broowiee is soPter ood has uoshared elevirve puirs whirl Tam perwit ‏ه‎ tot of Pour elevirves to portivipote io the bridged iva. a Boe? a) (he too & wore sire bridged ud wore stuble thao kydeoger bricked. b) (he bridued too vad be represeuied us haviey tu coudeut brads to browtee ued is elevirophiic but oot elevirva dePiviect. Advanced Organic Chemistry (Chapter 6) a. banaei 

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iad ۱ 2 0 ی ال (0) ناك با موی ‎bridged‏ iva The Wey? is ‏له امه و‎ ood strocdy poliziogy. ۱ polorizes the 7 ‏دوصكان وه خام ماع‎ to the exteot thot a theee-peuter, two-electo bod is Porved betweed wencury ocd the tw corboos oP the double bowd. MkerePore: ‎threeveder, two-clevirva bod tophes weuker bridge ta the‏ © (ه ‎the fhree-veder, Pou-elevirvd brody oF the‏ ما ما فصو ‎browostucr ion.‏ ‎b) Oxxvercuruivs oP stople dheuers ts wudly u sterev speviic ‏له‎ ‏.لله‎ ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

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Abn Qeurivip oP wercury sults: Gobvest Cousiter inst (CF,CO00).Vy > (CLgCOO), Ly > Wyk Got ssivas reduce the reuniiviy oP the Wey? iva ‏موی بو‎ wwhick reduce the elevirophiliciy oP the cotioc. Phe ‏تلا رت موه لوط‎ OO, unl O10, eae the wenn ipo in wore reuriive State, 

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6.5 Addition to Alkynes and Allenes ۲ ee eee Okt is the stereuckewistry aed reqiockewistry oP addition? Oovsidensd ‏:ع حدم تدده عدجا‎ x 7 ۱ + XY —_> wont ©. Soa 3 ‏سود‎ ‎٩ 4 6 R xv ‏و‎ ‎9 ‏تا ا مكمه‎ — ec ‏و مد‎ ~R 08 0" x ‏حب بلا + هممعمه و‎ pate — ‏من‎ ‎3 ‏یت‎ — ۳۹ al ~R Oeckwisws (@ unl 6۵ awe of the Od, © type white werkuisw 0 wand be chossiPied us Pd, 9. Advanced Organic Chemistry (Chapter 6) a. banaei 

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‎Ort Ovevledes ta BoOW‏ با ترا اه سل مق ‎Ar, R‏ ‎- ۳6 t= Ro cl H ‎“aN ‎Ar—C=C—R + HCl —* Ar— ‎Hoac “AN OR ‏حم‎ ‏یی‎ «H ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

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Clevirophiic Oxkiios Oly reviews: Ut cod be ‏لت )کید‎ xnktiioa) ‏عه‎ @OdgC, depeed vo iedvidudl structure ced reurtiza OW 0 = we 9 AO ie I NO-C=O—W ——> 10-C=Cee— 1WO-C=Cle ‏ااا )ديه‎ Golvest Isviope GPP ect: Protocaivg is rote detercviciccgy Gtep MO Oaloulativas: © pe SD¢Skeallvol is less stuble than = WeO-O=Olle, ‏با‎ Ww Advanced Organic Chemistry (Chapter 6) a. banaei 

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Ockhioa DP 0020001 ‏وا بت‎ ®-C=C-R + CROOOW ——> ‏“ين‎ = © oo 00 ‏با‎ 0 Goa acd acti Odditioa Aodurts Dre neuritic ure proceed throughs o vip! mative. 5 a 9 0 ‏حو" مود مهم 22% سممعمصه‎ Oe a crs 0 OW ۱ ۲ 20 + ©© - عبى م Advanced Organic Chemistry (Chapter 6) a. banaei 

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R-C=C-W + Oe —— Goa @dditiog Qoduct ®—-O=C—-R + AOg— Pati @dditioa Avduct (GDtiwes Paster u) D.G. ia deoh ‏ره‎ is stubiized by bok dh substitu. b) DG. kas ‏لعي كص‎ iva pRaruvter. © a ©) @-C=0-R + A 4 Boo = 6 ‏جر - ون جل ب‎ ۰-0 ace Se a. banaei Advanced Organic Chemistry (Chapter 6) 

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Apert O@rowieatiog ‏هار( ۴و‎ a) ‏ابو‎ awetlewes a Gz Q-C=C—W — =~ @ati @dditiva Qoduet QDeckuisw: Perwoleruar (Bd,9) BIO ieee eves 02 ee ‏ری رو‎ boat inne dre dees تأ تدج 7ج دجمج 1ك- و جر صادتلجوسصادا حكصادص أنروان عاب حها"!/ (۱۱ Advanced Organic Chemistry (Chapter 6) a. banaei 

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Veo} GPPect oF Or toa Oxkttiog vo Oeckacisa @Ohyee-browne vowplex: a) Ovlapsiey to bridyed ioc b) dissociative to vie cativa Wwheo the votive is stable. ۱ ak cuckophic (Pr) OL © 1۷ كو Advanced Organic Chemistry (Chapter 6) a. banaei 

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bin ‎oP -Wexeur tt BrOW:‏ هلان ‎Aa 0 ‎I ‏مايل )دم سه‎ oe oncloongcts 2 AOC Me OTe xyoe (pore ‏و وک و مس مالس‎ ‎OW,Ch:‏ ۰ وراک ‎oP‏ شمان ‎A [OAM ae Ae oe a a No ‎ ‎W-O=OC1Ig Mo ‏عموصاا-1 ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

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‎Oreveves wi (Or), tt PrOW‏ <و موس ‎Wy (Oe) oo ‏م2‎ ‎Ce‏ 1ه 2ه 22 ده ‎OW 2566 9‏ مان 0 ‎Catt @dditiog Aodurt‏ ددرودسر اكه ‎eT‏ وداه ) عاك — ۳-۹ سس ۱-0-۷ ‎GoW Om AbyORs‏ ‎Goa Odditiod Aodurt‏ ‎(Geetic: Pirst order io botk oko ocd Wx(OPr) 5 1 ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

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«الميام قد ‎Plkyurs:‏ تا ملل) لس له ابوزت) ‏له موی اروت اه تن ‎owrstierevepenic (depeudag upeo the tPe‏ ‎cuctephites).‏ عا خن ماه تور ‎ridged iva ttiercvedddie pr ‏:وص یی امومع واه‎ ‎sierevspevilic cat ‏له‎ ‎ 

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و9 ما ی( ع دعص أن ‎(Oxkdiiog to‏ );, Opt Ouran Ieterwednie Oil capa koe od (OAS ‏توص لا امطلمی!‎ thos caine wit sp? hybridization. her ant be poral ‏همه‎ by higher B.G. oP uhpors. b) Oricged too interwedkies! Larger rate retardatiza Por the ‏موه‎ caddiiza thaa that Por oheurs. Crevier destdbitzaion oP brikved spevies by strain ood ‏واه‎ ‎eb Pevts ia the cose oF ukpors. : 0 7 an yes ‏اس‎ less Ravored Advanced Organic Chemistry (Chapter 6) a. banaei 

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Glevtrophiic Ockdhtios to Cleves ‏اه م۳‎ 0 1 6 ‏عك بجورووحودروعم‎ ROMGO=CUR viupt puting (Protocaiiva ot vecticot 57 ‏را‎ 5 © ROUFO=O1KR ‏ملكت‎ ROLCIFOUR ullp! cation Advanced Organic Chemistry (Chapter 6) a. banaei 

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‎pe 0 2‏ ۱ لا ال ‏اماوسه ‎Potosatiog oPtke‏ أمتائط ‎carbs tutsied structure asd‏ ‎allylic coojuqution‏ عم ‎Dhe twisted cativa is about UP kool/eot kicker fo eoergpy theo the view ۲2 ‎allylic coajuyation ‏® + ا عم ىنهم هنك جورموحود ووم ‎vinyl ۹ ‎Porson is hiceticay Povored.‏ وی ابوزن) ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

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Ockdiica oP WX ‏ییا با‎ x Om=O=C1l,g — ‏ماک‎ ate ‏ما‎ ‎x x O@dkhtica oF Ore to Cleves 9 Rot 0 ‏مت ار‎ (۳ W 1 ott Ww CUR C-® | | Ou ‏را"‎ ullplic cation churavter Advanced Organic Chemistry (Chapter 6) a. banaei 

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6:6۲ ۴2, El and Elcb Mechanism Cheoivation ‏:مت‎ ‎1 ‎4) ‏سنج‎ R- 0 + WX o-elivicatiog R 6 Ww 9 ‏سس يروس اوم‎ ROUFOUR + WC B-elimicctiog © ‎R R‏ را ‎9 ROU OX > 7 ۰ ‏زر‎ ‎0 ‎Advanced Organic Chemistry (Chapter 6) a. banaei ‎ 

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:دصندد 0 :اهوم طوب()9) 1 8 م 1 با 1 ‎R _ RorourR + X‏ يما لج © + 0۷ ‎x Ky, ۷‏ 6 ‎oP B-protos ip‏ شم وه ار طذ .46.85 عواجوصاصكز8) ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

صفحه 360:
@I Devkasisw: W 9 ‏سس مج‎ ۷04 =—@> ROU-OUR + OL | x a ROG is the usicoolerutar ivcizatioa. Bch Derkusisw: Ww 4 ١ © 9 1 9 CO ae ‏سو ا‎ Nr ORO 1 x x dct QDeckuisw: The ‏توح‎ is ucievlevulr, lke 0 weohurisw, but the order is reversed. Advanced Organic Chemistry (Chapter 6) a. banaei 

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bin Ovi CO T.G. Thenry 4ooveastoy O-Wbreakiag to the TG. o- 9 x lob Glob ike eer cai ow we Aroreustay O-X breahiag ta the NO. ack Advanced Organic Chemistry (Chapter 6) a. banaei 

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2 3 2 & 2 0 = 1 0 ef i CHyCHEX Cox elnnvage — CHycite' + CHaCHX CH3CH2* +B B4Xx +8 ‏لها‎ (8) Fig. 64, Three-dimensional (More O’Ferrall) diagrams depicting tansition-state locations for El, Eleb, and E2 mechanisms. 

صفحه 363:
ourios t= Povored by: OP wok 3) ‏بحام دوا‎ y-vups thot stabliztay the carbocation b) ‏دصحي نمیا لس‎ v) Golvedt oP high imciziay strech Phe bose phy ww role in the ROG vf the Cd werkenios. Per Iociztion: Cowprticy reutiva (6,0 vs. Ed). ‎bose Puvor the Ed pak.‏ مسق ‎9. 60 ‏وه مرو‎ ore licvited to neurosis hoviey substituects ‎ 

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6:7 Orientation Effects in Elimination inet, Reactions (Regiochemist Ed Oeckwisw? bewioy youp is cowpletely ivcized bePore O-IW ‏لصا امس‎ ‎whick kus sowe double bood‏ روصت ام اه مهو و ‎is ۱ ۳ ۳ geet ee‏ ‎Ae ‏نم‎ ont ay gon « Ole ‎Advanced Organic Chemistry (Chapter 6) a. banaei ‎ 

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‎A, less substituted alkene‏ نا ‎/ B, more substituted alkene ‎Fig. 6.6. Productletermining step for El elimination. ‎ 

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Cdck Decks: ‏صما برط لحخشصصي جا مشمواه خن ومصفوصعل جا“‎ ruse. 6 ‏اور‎ oP the B-W (les hiodered side). 69 Oeckxisew: The direviva oP elevicciod is depeuds va the previse ‏وه‎ oP the T.G. ‎Ox:‏ الم ‎CWike Ex:‏ ‎Ourtable CO T.G. Very ‎ 

صفحه 367:
bin Gyuahows C0 Deckunisw: (Portal rupture pe O-W un C-X boas ‏له‎ ۰ artic! double bood character ot TG. Oore substitvted T.G. will hove yrecier stably (lrver every). (GuytzePP Rue) 

صفحه 368:
Table 6.4. Product Ratios for Some E2 Eliminations* Percent composition of alkene Substrate: re CH;CHYCH2CH, ‏)دا‎ Base, solvent 1-Hexene 2-Hexene x ‏سیب‎ trans 2-1 McQ, MeOH 19 a McO™, MeOH 33 F MeO”, MeOH 69 050: ۸۱۵0 ۰ ۷0۲ 33 1 ‏تمظع ,“رجام‎ 78 a 1-BuO~, -BuOH 9۱ F ‏امسقم ,“مهم‎ 97 0S0,C;H, BuO”, ¢BuOH 83 a. Data from R. A. Bartsch and J. F. Bunnett, Aen. Chem. Sov, 91:1376 (1967). 

صفحه 369:
ose ‏ارمس6‎ GPRevt Abin Table 6.5. Orientation in E2 Elimination as a Function of Base Strength Base (potassium salt) pK 1-Butene from 2-iodobutane? _%) 1-Butene from 2-butyl tosylate” p-Nitrabenzoate 89 58 ۰ Bonzoate 110 72 ۰ Acetate 116 74 ۰ Phenolate 164 114 30.6 2,2.2-Trifluoroethoxide 6 143 46.0 Methoxide 290 17.0 ۰ Ethoxide 29.8 111 $6.0 e-Butoxide 32.2 207 58.5 8. Prom R.A. Bartsch, G. M, Pruss, B.A. Bushaw, and K. E. Wiegers, Am. Chem, Soc 98:3405 (1973). The p& values refer to DMSO solution b. RA. Bartsch, R. A. Read, D. T. Larsen, D. K. Roberts, KJ. Seott, and BER. Cho, ft don. Chem. Soe. 101:1176 (1979). &. Not reported. © stoowner buses leads ‏موه موی وا با موجه من تا‎ uf the 4۳,۵, ‏لداع جه‎ tt to he 02۲ ‏سس‎ Advanced Organic Chemistry (Chapter 6) a. banaei 

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bin Gteric GPRevts (CAQCUCNCNO ——> (CAQCUCHECIO 4g + (CUQCICUOWRONG 1 Cube, OOO Meads ‏موص‎ ‎0) 9 0) 990 Advanced Organic Chemistry (Chapter 6) a. banaei 

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6.8- Stereochemistry of E2 Elimination jet, Reactions eon 0 x) N 0 los Se I~ ae weO— — C=O ‏سيك‎ aul wae ‎PN we‏ الل تي" ‎aati‏ كرك ‎a) Onstereowers reacts ‎b) Gterevspeviicdy deutercted subsirues ‎Advanced Organic Chemistry (Chapter 6) a. banaei ‎ 

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ee Gtudy oP The Gtereockewstry a) Onstererwertc reuctadis OTs, a ۳ ‏با‎ ‎Cy, 3 0-08 ‏وس‎ ‏را “و ركس"‎ Or De ‏ناك‎ ‎Oe Ww ۳0۵۵ O=0 GOW AR Oe Advanced Organic Chemistry (Chapter 6) a. banaei 

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دام عام فيد 01 ‏بو تقو تقو‎ > ‏لكر‎ ae oC 1 7 32 a 0 oO uu Ww oO Ww ‏“ريم‎ "۳-9 Zproduct 0 oS ‏تقو تقو‎ ۱-2 erythro isomer ‏)جر تن‎ ‏اا‎ ‏ب8)-ه‎ 1۳ 4 W E-product Z product Advanced Organic Chemistry (Chapter 6) a. banaei 

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‎[2p‏ ۰ سر ‎LT‏ ‏ع2 ‏ا ‏9 اد اد كمد وام 86 ‎atk DO ao? ‎Fd x ID a 0 a ODes ‎ ‎ ‎ 

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:م5 طسو9) انه سام ول یی جح عدندصا لوص عشب لحصصكة إجصم بالدموصصه ذا مصاددادوناج ) هار لت ‎us Or‏ yx ‏موتمم‌نمله‎ is bevowe isoporteat with poorer beaviegy ‏ای چم‎ us (PO oedd trivethyd ovine. Cxteat oP spo elvvicaive is fooreusiog wits tomreusiog the crater feuds. ۳ .أدمد جا ومقدوامكات ۱ wis O-kexd aed looger choices sya elevicative is prevolect. ۱ ‘Advanced Organic Chemistry (Chapter6) = = = a.banael — 

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Oter Pavtors ‎@resewe oF Pree bose pr toa pur.‏ یم ‎in departure oP the‏ نوت موی ‎ou pair proses syu elvvivaiog.‏ ی موس ‎wX Vx‏ ‎OG 4 s‏ تس ار 3 ۳ ‎ROU + OF‏ + 7 حك ور ‎٩‏ ‏~ به ۱۵ ‎0 ‎R ‎Cxtent oP ‏تمه مرو‎ is wool higher iat cowrdisspviniogy soled ‎beweve thao it DOGO. ‎Oddiica oP speviPic wetdkive-oowplexioy ayects (awa ethers) ‎Advanced Organic Chemistry (Chapter 6) a. banaei 

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ف 1 0 واه مرو ‎of‏ مسجت ع رال چا مس مسب ۵ سا ‎Os‏ امد 1 6 ۴ ‎ih‏ ا © ‎rm!‏ a (۷۵ ‏سح‎ oa Wb a! 0 a! ۴ 9۵ ‏مرو‎ % acti 0 OrO-Pk 2 ‏مع‎ ‎۳ (CUQeOW = 6 Ok Or a ve ‏لك و‎ 20 ee Advanced Organic Chemistry (Chapter 6) a. banaei 

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0 uuti puth 

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Mitesh (@ulkier Yup, ‏نباعه ادعوم‎ ureusulbroaes, ‏عرصدان ا نالل‎ 0 oP the vis-dheue. Odi Oda 6 0 Feil ۳ Kp at A ] ‏سه 0 ۲ ساوح ا‎ 1 1 > 6 ‏سي‎ © 6 Advanced Organic Chemistry (Chapter 6) a. banaei 

صفحه 381:
‎Dehydration of Alcohols‏ 6,9 د ‎ ‏رل را" ‎wv ee ee a‏ | ‎®-O-CAR ROO > ROWER» ROUFCUR‏ ‎OW Ole‏ 8 ‎Ed ODeckaisa ‏:عملم هه شون‎ ۱۹( substituted deur will be Pore Reuniivity oder oP ‏نامیاه‎ ‎9355-32-0 ‎Advanced Organic Chemistry (Chapter 6) a. banaei ‎ 

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bin هه مساو عاص سم سس سمم سب با © | هه + 0۷ حست 2-0-۱ 9 5 6 ‎ROCUR —> RO-O—R —> RO=ORR‏ ‎oy‏ Cxckange oP kudeoxpl ou: Oowpeticg oP God Advanced Organic Chemistry (Chapter 6) a. banaei 

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مسرت زاناس % aati % sya 10 0 0 ad 

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ا ا ل 0 52 د ۱ 1 | & Gm, 0 ما ی ور +۳ we’ ‏وه‎ > 7 ۷ Tre cuclevphiic ‏اه اموه‎ iodide ot coe browide euboues ‏كلا‎ Advanced Organic Chemistry (Chapter 6) a. banaei 

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bin ‘Viar~Ttedued Orbrowicration: Ovw-Gterevspevitic Porwetive oF ‏:الوا حممه‎ + ROWLCURS Is! __ @oiecur + OP + و Advanced Organic Chemistry (Chapter 6) a. banaei 

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ار رووروو() لحدرلهت لبوو) Atti | Ay Un, ‘Ty “eootg ~ — 8 oo + oxo ww" —_ 7 oN Ww ‏سح موم وم ول‎ ue wok wore ‏اه وا شوه‎ ‏عاصموان.‎ ۰ COW,CL(OW)CW, Wel is powered to propeu ueder uid ‏تم راون‎ at a rote IO" fees yrecier ‏مكلا‎ that Por ۱ the sue vosediios. Advanced Organic Chemistry (Chapter 6) a. banaei 

صفحه 387:
۱ 5 «الميام قد علطا جور جحصجدم)/ر وجو اجات جروجدواادو- 25-9 ‎froas~ acid‏ 1ب 4 ناك 2002 ‎Or Ay‏ ‎a‏ ‏یو()) ‎Ww‏ AQ? Por troos isower is obo © koul/eool tess thos Por the 7۶ ۰ Advanced Organic Chemistry (Chapter 6) a. banaei 

صفحه 388:
نک و ال توریب ‎POU,01,0%‏ ‎(Reuviivity oder:‏ ‎Vt = PkPb = PkGa > Pk Ot > WD‏ ‎Oocdd euerdies:‏ ‎WeyC=CP < Pb-O=010 < Ga-O=GSEF < GtC=00 < W-‏ C=99 ۱ ‘Advanced Organic Chemistry (Chapter6) 9808۵ — 

صفحه 389:
Gir carborsion ‏مصعم كات‎ od the B-carbod «tow ‏سل‎ rick O-@ boc to ‏سوه ع‎ p orbit or us Porwoiion bridged spevier). ee مه ض لا ٩ ‏ه‎ ۰ a. banaei Advanced Organic Chemistry (Chapter 6) 

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Clkvicaiog tc B-hobsicaes! cy | سلجا حرس ‎Og‏ تاد ىج جع كا حم كي | GQ ‏مصلدد اواك - 6 لس سس روت‎ 99 99 ROOOCHOUADES + RDP —> 0000 ORp + CleFClle + PADES ۵0-۵ BUS 4 ‏ه‎ ‎ee ‏جد‎ ROUFOWR + XC + De Gdn ( Advanced Organic Chemistry (Chapter 6) a. banaei 

صفحه 392:
Gtresy varboodiva coruter dt te Boowboa wow oo sites by old ced staaepl substiccais. © ‎ROU-OME‏ 6 يدن جل 20/۱ + & Ourbuniode choruster ‏موی لو ون له‎ character 0 OO 1 1 7 it COs © CULO ‏پآ‎ Advanced Organic Chemistry (Chapter 6) a. banaei 

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1 ۵ ۳ ۳ 7۸ و OO! OS Cc aes kl aD 

صفحه 395:
7.1 Acidity of Hydrocarbons ‏و‎ of he rebaive anid oP covet corboe acide i wore diPPiout, becouse they ane sv we uid. Oey weohly uidic solveds suk ‏جه‎ OOGO uc polvkent ide Ure use us solved Por corbosivd yeuerdiva. ‎syotew.‏ جوا ‎ke bosiviy oP‏ با نمی سوه ‎(Oxaloqous to the Weewett aici, Puoviioa W,.‏ ‎Phe vole oP W_ correspouds eesruticly to the pI oP strony busi aoseoquerus svluiivas. ‎Dhe forger volues oP IW, the yreuter is the protva ‏تاه‎ ‎bility oP the wediue. 

صفحه 396:
Ei Qsskpnved oP W_ to bose-sobed systew! 1 eet menses Table 7.1. Values of H_ for Some Representative Solvent—Base Systems® Solution 9۹ 5 ۵۷1 15.5 10 W KOH 17.0 10 KOH 18.5 0.01 M NaOMe in |: | DMSO—MeOH 15.0 0.01 M NaOMe in 10:1 DMSO—MeOH 18.0 0.01 M NaOEt in 20:1 DMSO—E1OH 21.0 a. Values are rounded to the nearer 0.5 pH unit; this is typical of the range of disagreement using different indicator serics. b, Selected values from J. R. Jones, The lonization of Carbon Acids, Academic Press, New York, 1973, Chapter 6, 

صفحه 397:
و 4 موسپیا ۴ (وسلس )0م) رطلت سا مس ‎kowwe W_:‏ ‎=H +log‏ ريام ‎dP tke ‏مشود وله‎ oP the ‏سس‎ ood uvivdic Poros ure ‏ماه‎ dPPered, the cowedroivas ve each oo be ‎ 

صفحه 398:
AP the ‏سید باه‎ oP the oeuird ‏ی لجی‎ Pore ure co svPRicieaiy ‏رسای‎ vor oP the indicators used ued its spevicuy is ‏.لوصو‎ ‎oP kydeocarboes ic terns‏ رل( :یله( ض!'[” ‎DP the relative stabilities oP oeutedl ced ccivcic Pores.‏ ‎4a woop cases it is unt possible to obtain equilbriue data. ‎ 

صفحه 399:
عا ,رصح ‎uo source oP‏ اه موم ع ‎eetepic Cxchooge: bo‏ موجه و ها لام مر ‎oP OD aioe isto oo‏ بملوسصووصصصدا خأم صاصر ماو موی اه ‎oP the rote‏ ‎OW‏ + ۶ د ۰ + را۲) ‎RO + ©‏ —— مت + م ‎)5 + ‏ركنم‎ =—=— 61+ © Phere is ceed a corretion betweeo the ‏لته تص‎ ood ‎]۱ Chemixtey (Cinagter F4 ee) 

صفحه 400:
ی ‎the corbadod of ow tkve. Phe‏ خا مومه طاطم جيه و ‎oP porbosica Poreoiiva is judged Pro the rote ut‏ وه هار ‎whick exckoage vous. Dhis wethod is therePore ts upplicuble to‏ very weok uvids. ‎oP hectic weeweweds! cowplicaiva due ty the Pate‏ ونم ‎DP the iow poi that ts Porxved.‏ ‎4P the iva puir seporctes ‏اون وا امن‎ the svlutice rapid, sv thot euch ‏مور‎ resul ic exckouge, the exckooye rote is ‏مه‎ ‏موه وا موجه هجو‎ 

صفحه 401:
@usts Por Osiag Keetic Bridiy Data ری بو ی سب سوه تس رس ی چرس ‎eet‏ یس ‎cea con‏ ()) ©9 _warzuios 6 © 9 ROW + OO : (ROO + ‏42ج) له إل‎ + O + OW ee ‏اج‎ ‎4 ‎ROO + & Qu euddewe ۳ ‏اوه بصن‎ ۱۰ Qucewizdive without Caokoage of Okirdl Crater ]۱ Geqawminc Chemixtiey (Cinagter F4 ee) 

صفحه 402:
۱ Oeroeend Revere Gove Prtany: Io0 poirioy is yreutest io o-polar ‏اه‎ such us pers. Ia dippkr soveds , awh w DOGO, Girwture: The ideotiy oP the coliog preseot have ‏امین‎ ‎eR ect iP ioe poirs one presedt. 

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Dre rote oP tite ‏تج رهطم‎ avid) Por o ‎WwW Ww OW‏ بلك ‎di-beuzvhuvreue di-beuzoopolokepiutrieur ‎]۱ Geqawminc Chemixtiey (Cinagter F4 ee) 

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۳ ۳9 ۱ ‏تست‎ ‎ee 124 ‎uwiue)‏ انودع كا اصبرص) 

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‎XK = FO‏ :(صس-) راب ‎Cottwoted oa the bose oP ‏ما موف‎ a perice ‏.عدم باص إل‎ ‎Cty: pK = PO ‎sass‏ بت 

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اعصعك لحه ننصاك صما طز عوج حاصو :سحام وراك لحك © 1۳ ‎uitues is ut Peusible.‏ ع اس بو Crow this volue ord komad O-1 boo dissociation ۳۱۳۲۳۲ ۳ votes oa be esticvoted (seni ‏جمالك نی‎ 0 = 7 :امه ]۱ Geqawminc Chemixtiey (Cinagter F4 ee) 

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sp Wydrogess ۰ ‏ار(‎ with the large deqree oP = choructer (GO%) ۴ ‏لحصط رلاکزر)‎ Dre op orbital is wore eleciooeyive tho sp? ocd oy 

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1 ae Oe ‏اح‎ ae ee > ‏نموه‎ bood cate ‏جز راك دراك خاص‎ 922-0000007 Corbusivas ure predicted to be pyramidal. 4a plowar varbasiva, the LP would parupy a p orbital. ‎yevswetry, the orbital woul kave substoctict‏ لووسم و ‎vhoruvter.‏ = ‎Ginwe, the L@ woud be oP lower esergy in oo ‏اطع‎ ‎wis sowe = choructer. 

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7 Gterevckewetry oP ‏مارا‎ Cty OW 57 | ‏را‎ Ore 5 ow | OUPAe—C- C7 CU Ape CUNO ‏وتام احج یج‎ | ‏مان‎ Ok ‏ها‎ ‎+ ‎Optically @rtive CAM 1e= aol 0 ‎cous soles: Reteuivg oP coor icpucaioc.‏ جشفدصاعتك بصنا ‎| the awoudt oP imersiod wits 1۳7۷۳۵ the ‎]۱ Geqawminc Chemixtiey (Cinagter F4 ee) 

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‎Ei Buse! -) 8006‏ حجن بحري 0 اجه اه مها اصن 95956 ‎Por the vorbosiva ito fight ima pair, Curb‏ ولصتا حصا ‎vr‏ )با با تج ‎ves wt sywwetricdly solvated bePore‏ ‎keto.‏ ‎Owe: KOW Gove: Cthytece Clool ‎Golvest is a yood proiod source ocd the proivociivd wut be ‏موی و كد وه‎ soloed species that Payor 

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‎t-Bu‏ :صص) ‏0 :مساق ‎dOO% Ruvesvizaiiva ‎Por the vorbusiod 0‏ ما لاله 

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ادح ۹ 6ن 8)- ه) ناكف ©)- :راو تیه ام موه عكلا صا ملس جوا ‎o svlvect‏ نت و و ‎doa pair‏ ‎wed iva aris us the proiva doar.‏ ‎Owe: +OuK‏ ‎Covedt: DOGO‏ Ruvesrization Gpyeweticd savaivg is achieved prior to deuterciva. ee na) ‏و‎ 

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:علي مم7 3 ‎OClldi + Li‏ سب زره + کال ‎Oi + ۲‏ بت ‎u-Bu@ + Bi‏ ‎PRO + Di —$ gli + ‏)زرا‎ ‎Olkough these poswwpounds Kove sowe voudedt chocuvter, ‎]۱ Geqawminc Chemixtiey (Cinagter F4 ‏شاه ود‎ 

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۳ ‏هلا و ولج توت هط‎ 412 ‏ااا‎ OW sbi > eOwWi > HOW Orprotociva oF PkK-OW, by Oui is thercvodyoavicaly Pavor, but the neuriiog is quite slow ia kydeovorboa us svlvedt. Orew likes exist us teienver, hexnwer ood higher ‏اه لو اسلا و مره‎ soleus. hese spevier vo be studied by low tewperaune (DOR spevirosvvpy. 

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2 1 I us; + FCIQGDAMADA) ‏احج‎ Ps 2 ‎Tetrawetkplethvleaediawice 5 22‏ — رکه ‎(THEO) WO 7S ls‏ ‎(PRU is teteaverto ‏دز‎ )0:© ether - pyolchexcoe, but disveric in d:9 ۰1۳۵۵۶۵۵ - ‏ورن‎ ‎]۱ Geqawminc Chemixtiey (Cinagter F4 ee) 

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ACA i VARA bi x 7 NNEC ON tetrawen structure (distorted cubic) 0 1 ‏بلالا نوست ورا‎ I Cll Cl ! Li-O— Cl, WD t 0 WO QSOlubtobipkeapl bithtuey pheaplavetylide (comple med wath WDD) (cowplexed with o diac) To a ee) Ce eda a ee 

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‎Stabilized by Functional‏ م ‎Groups‏ ‎(oS a a a ‎Order Por oxive stubiizativa: MO, > C=O > COZR = GO, = CO < 00006 ‎ ‎ 

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ات تس 

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‎of O =O vowpourds.‏ ا میس ‎of ‎ROWR + @ Ay RO-OR + OW ao I 1 0 ‏مه‎ + Xo ‏حتت‎ oe + xX ‎x ‎]۱ Geqawminc Chemixtiey (Cinagter F4 ee) 

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4) ‏حم ود‎ )0 ‏عم ([) بجنس جوجححامك جدرصادد!» :وصتدحو اصع‎ 4١ O 0 ll 06 ١ ا 9 0 ١ 1 RO=OR + GO ]۱ Geqawminc Chemixtiey (Cinagter F4 | 

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}. Relative Rates and E, ۵ ‏سور‎ Deuteration of Some Ketones R i ‏)یلاع‎ ریز ‎exshange in NeOD. T. Niva M. 1‏ مره ما 

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= Rote oP deuteraiza oP sicople uly betas? CL, > ROW, > RZCW Gteno Kierdeoe to the opproock oP tke base is probobly the ۵ Pacior. ) ‏میس‎ @PPevs va The Que oP Orprotocaicn Orr strony bases suck ws LOO o WOOG in pokr ‏وه‎ ‎svlexts suck so ODOC ow MLE ques soltioes oP the euvlites ‏متسه تسار‎ rePlert the rote oP orexpoud oP the diPPerecct proteus te the vosparetricd O=O cow wpournds (hicetic cvatrol). Mke feast hiodered proioa is newoved worst roptdy ueder these coordiicas. Cor wspeowetricd hetowes the kivetic product & bess substituted 

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نو عا ماع اون جكاا و لمم و و ‎the vordous euvlotes oP‏ ‎eae‏ نان لا را سروه Idea cowdiicgs Por ‏و اوه خر ام ند‎ one those ia ‏لوح وود كاعكاسد‎ quoctitoive, ced ineversible. ‏:لسوت‎ ‎a) Osteg very sirvay base suck us LOO b) Oprotic solvent v) @bseure oP excess ‏تا‎ ‎d) Low texpperatire 

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تسش سس 

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Scheme 7.1. (continued) Enolate mixture 6 9 Kinetic LDA, 0°C Them العا رل -CH(CH)2 CH(CH)); ‘i cH. ‏و يد‎ cH 0 ion by D. Caine, Carbow- Carbon Bond Formation, RL. Augustine 

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۴ CR Reece ‏سس‎ Den at ee Dare ‏بیان بسچ‎ Dppusie respowwses 7 dhy! subsituicd. Thermodynamic Kinetic acidity acidity k(M~ min7') pK CH,NO, 238 10.2 CH;CH,NO, 39.1 8.5 (CH;),CHNO, 2.08 77 

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خا توا ادوس عطا کات ‎reversdl‏ و( ‎Qeaviow:‏ بو( موه ام و Cosiugate base oP 1, 9-dihicae (pK=S0 ia pyelchend ovine): CO یی + 6 و یت اهب و زرا ‎WwW‏ را" را باه 91 وشات لاهسا ده مشب( (ه b) DOT: Oryaive charge delovalizativa ‏و اه که نامه‎ )- G bow. ]۱ Geqawminc Chemixtiey (Cinagter F4 ee) 

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R > 9 ٠ 0 ‏ده‎ R ic? preferentially ROT1GR RONG ll ۱ 5 0 ]۱ Geqawminc Chemixtiey ٠ ‏+معجعهاء‎ 1 1 

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Chosphorow ond GuPur ‘ides VBE! Doles Por whick oor oP the poutrbuieey structures hos اواج © 6 0( صعه ۶-0 ‎Ckvepkouiuw ide‏ 0 0 1 9 ‎ere <— )< 7‏ ‎Galfoxociucw “ide‏ 6 9 8 دوجم سه بج يهم Gaulfouiue “ide ]۱ Ceqaminc Chemixiey (Ciragter F4 a) 

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9 © © ACle— PR =e ‏سج‎ @svspkociu;w Galt Ckospkouiuew Side ‎base © ©‏ جا وى حجتت ‎RECUR‏ ‏نا مایق با یه تانق ‎0 ‎ll buse "۷ Il 9 RO— ‏بل تقى" سب‎ ‎6 ne 9 ‎ ‎Gilfoxociue Galt Giboxosiuw ‘Side ‎ee rae ka) ‎ ‎ 

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۱ sone ‏ای موه ۲ اه 9 راض كمد كا‎ de tke ‏مت متا رجه خاو و2 تل‎ the cove sats are ‏اس‎ bese ucidis ۱ buses suck os uvide iva is required. © reaq 9 © OMe FR ~— ROU PR 0 0 ll base ‏ا‎ 6 ‎CIR‏ ويج حت چیپاال ويم 8 ممق ‎Giloxvaiud Galt Gioxvctud ‘ide ‎Dke oddiica vP O utoe io the ‏ووو“ انك‎ sults stublizes these plides pousiderably relaive to the slPooiud ylides. ‎]۱ Chemiztiey (Chapter F4 ee) 

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7.3 Enols and Enamines Corbowt cowpourds os curlepphie ta ucidic wed! uot Porsv: 0 ®ow OW POOR rh ‏مه ححه‎ 0 + UW OW eae 5 6 6-0۷۸ + ‏حب أن‎ ag = OUSR > oho or + ee e ‏و‎ ols ore wt os reuniive us rorlote iooe. ]۱ Geqawminc Chemixtiey (Cinagter F4 | 

صفحه 437:
Cxptzaios Oevkaniew: = Exckone oy ‏سر‎ & Ow تس ‎Pot‏ ‏+ سای و Qeusurtay The Rute oP ‏صوص عساو راك :متام‎ 9 kg OW 8 0 Il 10 I 3 Il RCCL === _—-PO=ONR ‏جك‎ RO-OUR + WX kag 95 ١ xX kor kg ka ‎ee)‏ عمعوعداء1 ‎ ‎eur cae 

صفحه 438:
7 wits base votdyzed rewoud oP proiva, the uvid ۷ ‏و امعم و الوصا طا موم‎ oP the wore ‏.اه لاله‎ 

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spel Pke ‏مومت‎ oP ewl presedt in ‏نانچ‎ wih ‏ه‎ 020 ‏حول اه با اوه محر‎ youps. ey stale ketowes, ddehpdes, or esters, there is very lithe ‏خن‎ the evl peesedt of equilibrivea. 9 9 O © = AA c ۵ الا لديل ‎So Os‏ ما ee) ]۱ Geqawminc Chemixtiey (Cinagter F4 

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۲ 5 i ‏مرسمه سه موه‎ ey 

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GPPevt of Govedt va the Exteat oP ‏ام‎ Porc 1ك با ‎fi tl‏ هن 0 0 60 ‎١‏ سپ = ‎ng ye 9 19 S00‏ يي لذ الم ۷ ‎Covet Gul Pore (%)‏ ‎COL. 4900‏ ‎veto 96‏ ‎qd‏ صه() ‎the‏ منم ‎W-boed io the pool Por‏ ولمم مرمصد ع۳» ‎wolecutar dipole by reduciog the oeyaive charge oo the oxyyed oP the‏ ‎I=O you.‏ 4a the wore polar svlvecis is lees iepportost, cod it protic ‏اه باه‎ we woter, W-boodiag by the solved is dowiecat. ]۱ Geqaminc Chemixtey (Ciragter F4 ee) 

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is ‏ی‎ hich Coweurutiod: Ortustuble spevies OO: Wl tPe at -CO °C is sever hows WaolP Pe ot +20 °C is CO wicutes ‎ODGO ur OOF, it whick the rate oP exchoe by‏ و سا سوه ‎4L-biediog is slow, «wetustuble euls have‏ ‎ 

صفحه 443:
Grveruiod oP Curls oP Grople Ketoces to Outer: ها ماما ‎oP euwkie soliion to wer: The isitol‏ مرلو ‎ost O cow, yeurroiog the eal Pore. (Cetvcizaivd rote‏ موم ‎depeuds va pI.‏ @ord Cupzed Qetoczuios! C-proiveaiva cowerted wits O- deproticatica (Geueral uid matalsis) ‏سرام‎ 0 ‘We 5> 0 I © ‏كيه + وله ج هه اد‎ + © ‏ناك ناك‎ )9 ‏لجورر ودج وي‎ (eicizuive: O-protocativa oP the eavtote 9 ‎Ww 9 (0 0‏ حرا 9 ذه .1 ‎‘on‏ سس ام م لون ۰ ۵-0 ‎ «‏ م - ‎٩‏ ۰ 2 ۷ 07 0 1۳ م ]۱ Geqaminc Chemixiey (Ciragter F4 a) 

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Gwk we wore wide thos ‏یه‎ 0 0 5-8 ee 4 wa NG ۱0۹ 4 Nee 10 Ow of on 08 ‎١ I 1‏ 1 لها حته واال۱0/۵0 0۵0 سح 01620۷ ‎ao"‏ 8 0-0 ‎ ‎ ‎ ‎a ‏هه‎ ۱ 3 ‎ ‏ارج 07 تمدع جم ون 1۱ ‎ 

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1۳ 

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94 مام الى ا مال Qwaugly Pavored W Qene Pepulsion ‎Chemistry iCinagtes ١‏ ممعم افيه 

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7.4 Carbanions and Nucleophiles in S,2 Reaction Ourbosivas one vB curkeophtes. Cuideuer Por 6,8 type werhuniow: Rewioa of O-browsbukee! «) ‏متا ارم امه ار‎ ‏م0‎ nuersiog oP podPquraicn b) ‏بر‎ ‎Qwewizaiod ‎lihivey rectcputs wih‏ حون تن مرش ‎process! the‏ موق مرها ‎hla, reagects cooreivebly poco ot cay oP‏ 

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> 

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حي وز سه ‎(jp‏ ۳ ات0۵ + رب 5 Oo ‏حبست مایمن + رد‎ CO | 

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‎O-‏ 60 نت ات ۷ 0ل يمسر دممح ‏۰اه ارواه-ز) عرج* ۳۳2 ‎elevirophiles‏ بعام5) 

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WOOO oP ewhkites kwe ‏ا) موس‎ oP ‏سای‎ oo 0 000 ٠ ais ۷ اوه و اه سول ‎Ooitk tetrocerio ond‏ ]۱ Geqawminc Chemixtiey (Cinagter F4 ee) 

صفحه 453:
‎the deqrer oP oggrequiod.‏ صا جلدم مت سل ان ‎a) @ddiica oP WOR, crow ethers or sila cowplextcy ‏رن‎ ‎DV he rote wreleraivg oP euhte dhyltiod reac. ‎b) Ose oP dipolar ‏وت‎ solvents (2.9. DOP, OOGO in place oP MLE): ‎he rote weleraivd oP coche dhyvhiicd reuiiod. v) CPP ect oF wetdl cotva! Reariviy order OrOy > Lit > Oat > 0)* Oroordiag the order oP dissovidive oF ioe pote ced ‏هروه‎ 

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ی ‎eb‏ C- versus O-cdhyhaioa a) Oddiica oP WOPO, ceowe ethers or sivviar ‏مامت‎ ‎ypu: eoreusity the O-dkyhatiod product. b) Oik the ooh lewiny yours swh w Or ud T CO-ohkylativa is the weir poswapy. 

صفحه 455:
وبا Solvent -BuOH THF HMPA HMPA HMPA HMPA HMPA + CHs—X —— Leaving group, X OSO,C;H 0500۷ OS0,C,H, 1, oso, a Br 1 

صفحه 456:
Gterio und Gere plevircws OP Pevis #66)! (Beplates that are ‏:كام مره 9 مور‎ uxiul Ny Oo 5 ۳ ]۱ Geqawminc Chemixiey (Ciragter F4 | 

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۱-0 ۳ Favorable: ]۱ Geqawminc Chemixtiey (Cinagter F4 ‏شاه ود‎ 

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Ravored i W R ‏با‎ ‏ال يدم‎ 0 \ ۲ disRavored +معمهداء مله جعطا؟ عتمهيو 20 ممعم ۱] 

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END OF CHAPTER