CHAR. 6] ALKENES 107 6.6 SUMMARY OF ALKENE CHEMISTRY PREPARATION PROPERTIES 1. Dehydrohalogenation of RX i RCHXCH,, RCH,CH,X + ale. KOH, (a) Hydrogenation 2. Dehydration of ROH Heterogeneous: H,/Pt — RCHOHCH,, RCH,CH,OH + H,S0, Homogeneous: H; Chemical: (BH,), CH;CO,H™ 3. Dehalogenation of vie ~ Dihalide (8) Polar Mechanism +X,-RCHXCH,X (X= Cl, Br) 4. Dehydrogenation SSE + BK RCHXCH, of alkanes WSS: H,0-> RCH(OH)CH,X +H,O—> RCH(OH)CH, RCH,CH,, hest, PL/Pa eee 5. Reduction of RC=CR, +BH,, HO, + NaOH— RCH,CH,OH 4 dil, cold KMnO,-» RCH(OH)CH,OH R-CeCH +H, ren ah + hot KMnO,-» RCOOH + CO; or Nareaths '+R'CO,H—"> RCH—CH, a ‘o + RCO,H, H,0* ~* RCH(OH)CH,OH ‘+ HF, HCMe, “+ RCH,CH,CMe, + Oy, Zn, H,0—+ RCH=0 + CH, =O (c) Free-Radical Mechanism + HBr—> RCH,CH,Br '+ CHCl, RCH,CH,CCI, +H" or BF, polymer 2. Allylic Substitution Reactions R—CH,—CH=CH, + X,——+ R—CHX—CH=CH, Supplementary Problems Problem 6.37. Write structures for the following: (a) 23-dimethyl-2-pentene (h). 4'chloro-2.4-dimethyl-2-pentene {e) allyl bromideCHAR 7] ALKYL HALIDES 123 Table 7-1 Sat se ‘Steps Two (I) RX A Re eX One: R:X + :Nuv — RNu +X" — or RX +:Nu—> RNuUX yr ecu Me Nut | oF RK + NUT — RNU +X or RX! FNu—= RNu! +X Rate = HIRX] (Istonden) (RXINUT] nd-onder) \e os aa TS of slow step Ex Nur “C-- (with -Nv> \ Molecularity Unimolecular Bimolecalar Stereochemistry Inversion and racemization Inversion (backside attack) Reactivity Structure of R Bare rsch CH, =P > Po 3 Determining factor | Stability of Ré Steric hindrance in R group Nature of X Rl> RBr> RCI> RF RL>RBr> RCI > RF Solvent effect Rate increase in With Nur there isa large on rate polar solvents rate increase in polar aprotic solvents Effect of nucleophile | Rt reacts with Rate depends on nucleophilicity rucleophilic solvents > Br > Cr RS" > RO rather than with ‘Nu Equilibrium ies towards (solvolysis) except when weaker Bronsted base RY is relatively stable Catalysis Lewis acid, eg. Ag. (1) Aprotic polar solvent ACLs, ZnCl, (2) Phase-tansfer Competition, reaction | Elimination, rearrangement Elimination, especially with 3° RX in stong, | Bronsted base Problem 7.12 (a) Give an orbital representation for an Sy.2 reaction with (S+RCHDX and :Nu if in the transition state the C on which displacement occurs uses sp? hybrid orbitals. (b) How does this representation explain (i) inversion, (i) the order of reactivity 3° > 2° > 1-7 < (a) See Fig. 7-1 () () The reaction i initiated by the nucleophile beginning o overlap with the tail of the sp” hybrid orbital holding X, In order forthe til to become the head, the configuration must change; inversion occurs. (i) AS H's on the attacked C ae replaced by R's, the TS becomes more crowded and has a higher enthalpy, With a3° RX, there ia higher AH? and a lower tate Problem 7.13 (a) Give a representation of an Sy TS which assigns a role to the nucleophilic protic solvent ‘molecules (HS) needed to solvate the ion. (b) In view ofthis representation, explain why (i) the reaction is fistorder,129 cuar 7 ALKYL HALIDES Table 73 EI 2 steps i | Two) Reet Be eo mi imi LI bt Tansion sates | bese wees: de solvent Be Il WB aga Indias E Tacs E2 Kins Fistor Second-order fate = HL) Rate = ARLE] Tonznon determines rate Bimolealar Unitolecalae Steeochenisty | Nonstecoapcifc cot! Ein Gr when ant imposible) Reactviny der Bea 2r> RX Be > 2 > PRX facor Suaiiy of R* Sabi of alkenes (Saye rule Rearangenens | Common None Dewan iotpe | None Observed eft Competing reaction | Sul, Sx? 52 Regiowsectvny | Savett (eee Problem 733) Favors El Fvor £2 ‘Ak goup Borer yorer Toss of H Wo effect Tnsrased widiny Base Seng | Weak Stone Concenation | Law igh Leming group | Weak bass > Br > CI" > F ‘Weak base Pope cree Cats Ae Phasetanaer Solver Polar proie Polar aproticCHAP 7) ALKYL HALIDES 131 u wh eee i wey Hh, enantiomer (RR) ‘rans- oF (2)-2-Bromo-2-butene Problem 7.31 Account for the percentages of the products, (i) (CHs)sCHOC3Hs and (ii) CHyCH=CHp, of the reaction of CHyCHBICH, with (@) CgHONa/C,H,OH > 79% (ii) +21% (i) (0) CaHsOH > 3% (il) 497% () < (@) CHO is a strong base and E2 predominates. (b) C:HsOH is weakly basic but nucleophilic, and Syl is favored, Problem 7.32 Account for the following observations: (a) In a polar solvent such as water the Syl and El trations of a 3 RX ve the same rate. (6) (CHC HyO -+ (CH) COM HHT but (CH) CLE OH” > (CH, }C=Clh +10 + Table 7-4 Favors E2 Favors S42 Structure of R yer>1 Persy Reagent Strong bulky Strong nucleophile Bronsted base (eg, MexCO”) ‘Temperature High Low Low-polaity solvent | Yes No Structure of L I>BroCl>F | I> Br>Cl>F Favors E2 Favors Sul Structure of R so7r>0 eee Base Strength Strong Very weak Concentration High Low Structure of L I> Br> CSF | I> Br>cl>F132 ALKYL HALIDES ICHAR. 7 (@)_ The rate-controlling step for both EI and Sy1 reactions is the same: RX Re Exe and therefore the rates ate the same. (b) In a nucleophilic solvent in the absence ofa strong base, a3° RX undergoes an Sxl solvolysis. In the presence of a strong base (OH) a 3° RX undergoes mainly E2 elimination 7.4 SUMMARY OF ALKYL HALIDE CHEMISTRY PREPARATION PROPERTIES 1, Direct Halogenation 1. Nocleophilc Substitution + OH —™ RCH:CHOH Akohol CCH) ——> CuHSCHLC CoHSCH Ct + SH” ——™ RCH,CH;SH = Mercaptan_ (CHysCCH, ——e (CH ,CCHICL 4 CN > RCICHACN Nite © OR” —* RCHCH,OR Ether 4+ SR > RCHCHSR Thicether 2. Replacement of OH in ROH Ni ——= RCH;CH;NH}X” Amine salt RCH;CHjOH + NeX + 1:50, NR —= RCH;CH.NR}*X" Quartemary in . Uy" ammonium sat(Q*A") * — — + R'COO ——= RCH;CH,OOCR’ Ester + SoCs Rewscinx SKE Retin 4 Mg > RCH:CH»MgX ~ on + LiAIHy —= RCH:CHy + PK 3. Addition of HX to Alkene RCH=CH, + HX—=RCHXCH, RCH=CH: + HBr 2") RCH,CHBr 3. Elimination + ale, KOH —= RCH: 4. Formation of Organometal + Mg = RCH:CH»MgX Grignard reagent + Li = RCH,CH:Li Organolithivm reagent Supplementary Problems Problem 7.33 Write the structure ofthe only tertiary halide having the formula CsH,Br, < In order for the halide to be tertiary, Br must be attached to a C that is attached to three other C° ‘This gives the skeletal arrangement Le, to no H's involving four C's. A fifth C must be added, which must be attached to one of the C’s on the central C, giving: t pene bs154 ALKYNES AND DIENES: [cHaP.8 87 CYCLOADDITION ‘A useful synthetic reaction is cycloaddition of an alkene, called a dienophile, to a conjugated diene by 1,4- addition. Ath oh f TE ieatder HE, HC, da, DiebrAlder reaction ‘cH cH 1.3-Butadiene Ethylene Cyclobexene 8.8 SUMMARY OF ALKYNE CHEMISTRY PREPARATION PROPERTIES 1. Industriat 1. Addition Reactions 2CH(-3H2) + HCH + cuy,.¢1 — #:¢=cH—C=cH + Ho/PUPb) —~ RCH=CH; (syn) ‘Na, NHy —* RCH=CH2_ (anti) + HX —- Rcx=cH, * Rex,cHs + HOMUHg*, HY) —= R—CO—CHs Yj ~ RCX=CHK "2. REXy—CHX: Yes 2. Replacement of Acidic Hydrogen + NaNH; — Re — + Ag(NHy)? —= RC ——~ + R’MgX'—~ RC=CMEX + R'H 2. Laboratory (@) Triple-Bond Formation Dehydrohalogenato RCHXCH:X or RCH;CHXp + KNH, ah (0) Alkylation of Acetylene 8.9 SUMMARY OF DIENE CHEMISTRY PREPARATION PROPERTIES 1. Dehydration of Diols 1. Hydrogen Addition HOCH; —CH;—CH,—CH;—OH /— +2 — Butane / 2. Polar Additions. 2. Dehydrogenation (Industrial) \_211,0 +Cl —= 12: + 1,4-Dichlorobutenes Athans: CHsCHsCHCHy-2Hy + 2h: — 1.2.34 Tetrachlorobutane C CyHf. ‘Table 11-40) Reactions Ethyltencene | Styrene | Phenylacetylene Bry in CC, (is decolorzed) - * * Ag(NH)F (forms : a precipitate) 11.5 SUMMARY OF ARENE AND ARYL HALIDE CHEMISTRY PREPARATION PROPERTIES ‘A. ALKYLBENZENES 4. Direct Alkylation 1. Oxidation ArH + CH, CHa X 2 + C10; Ch— Ar CCH, AML+HsC—=CH: Se, +KMn0, —“* a¢—COoHt AH +CH, CHO a 2. Reduction 2 Coupling > a ain CH,CH, At, CuLi #RX (1°) ——— — R,Culit AX — 3, Substitution (2) Side-chain (Free-Radical) +Cl,2+ ArCHCICH, \ (©) Ring (Etectrophitic) \ + X2 + op-CHsCgHuX — + HNO, op Colts CeHANO: + H,S,0; —=0-CiHs CoHsSOy Ht FRX AS op CHSCOHAR + RCOCI A CoH CoHACOR 4. Disproportionation \— + atc, cotter Cots (Catt): 3. Side-chain Reduction ACH=CH, +H: AtH + CH,COCI(AICI,) — Ar—C—CH,226 AROMATIC SUBSTITUTION, ARENES [cHar. 11 B, ALKENYLBENZENES: {Dehydrogenation 1. Reduetion AVCH,CH #1y—+ ACOH, 2. Dahyration 2, Oxidation AICHOHCH or ArCH,CH.OH A /_—— 2H Kno, —~ arcocson 3. Dehydrohalogenation ArCHXCH, or ArCH,CHX + ale. KOH’ 4. Dehalogenation ArCHXCHX + Zn ee Other Addition Reactions St S 4+ Xj ArCHXCHX + H;O— ArCHOHCH, + HBr— ArcHBrcH, + HBr-222 ArCH,CH,Br C, ARYLHALIDES 1. Nucleophilic Displacements 1. Direct Halogenation 7 + NaOH 225 ArOH + NaCl Art +X, — SS = 4+ NaNH, 25 ArNH, 4H1Ci fat? an Sat eee ee am NE AeA, AN X> a ait a ails ti ati 22 acinon \ +Cu— Ar—Ar + CuX, Ullmann Reaction \ 3 Electrophille Substitution. + HNOyH,S0,—= op-XC,H.NO, Supplementary Problems Problem 11.39 Write structural formulas for the principal monosubstitution products of the indicated reactions from the following monosubstituted benzenes. For each write an $ or F to show whether reaction is SLOWER or FASTER than with benzene. (a) Monobromination, CsH,CF3. (b) Mononitration, CyHsCOOCH. (c) Monochlorina- tion, CylHsOCHs, (d) Monosulfonation, C,H. (¢) Mononitration, CsHsCgHs. (f)) Monochlorination, C,HsCN. (g) Mononitration, Cll.NHCOCH,. (A) Monosulfonation, C,H,CH(CH,)CHsCH, < > ae a -m-Xylene is most reactive and sulfonates at C* because its CH reinforce each other [Rule 1; Problem L1.16(a)]