Ch.6 (from Alkyl Rxn Summary Ch.5 # Halide (from Alcohols) R - + oH KX R- OH R- OH R - - HORR R- x, KOH x + SOC12;R-C1 PBrs;R-Br + R-X SO2 HCI + R- x + So I HzPO4 can 20Hz0+R - R- X OH partial KSH - c c - + - y R x + KCN Dmso -xic c = X:8 R - xNaNs;R ethanol /water R - x IT = lky) A Halide - Alkene + - - Use to - x - 1) M50 y Base Ant:Rxn minimize to OR & se W Bulky and S ulforate -> Alkene O on one X: ⑦ Vox- H-fetsi NoH c - =c L over over SNIISr2 E2 /Bulky Base E2 Bases for Oppo-Markornikov toH X:0 Sv1, Sr2, El, or ER? 3 EL/EI over SNI = Bulky + EI/EZ 1SO2 +,0 c X:0 Rearrangements & Carbocation Hz0 10. ~ oH Nz 2E2 EI/E2 Dehydrohalogenation H + (N + iR-I+ - Alcohol - AlkeneEI/EZ Dehydration H-c-k-or HsPoyc c - Alkyl Iodides -> Alkenes x +R -> rearrangement + X:0 Alkyl Azide: E = NIN-R 2 aitser's Rule & Trans Elimination + ↑ SNZ net inversion & carbocation D X:0 (Nitrile)C-C Ether Inf H30 R SH - ethanol/water backside attack simplified + Alkyl Cyanide + Ch.7 ( to Alkenes - acetope/wateR-00R ↑ R'oNYR-OR' R'OH +x. 2R'OH have / - Alcohol 2H Sa2 has x - Thio pyridine Solvolysis + - x:0 + RCOK - R x OR' ↑ iSulfonate Halide - Ester > Alkyl X:* 0H + ↑ MsCIopTsC;R-Ms(orTs) OH - Ether Hz0 + x + Alcohol DMso+R ↑ pyridine R- OH R- R > Alcohol Sr1/Sw2 ↑ NaOH -X R SNf/Sn2 AIcohol - Alyky1 Halide Halides) over Sn2 Ch. 8 34j -c c-c-Y ↑ X- (from Alkenes -c c- Addition AIkene - Alkane Hydrogenation c c = I + (Syn) H2+M( H H ↑ ↑ 4- - - -> P+, Pd,Ni, Rh AIkene - Alykyl Halide Electrophilic Addition =c- HX i- CHCls Alkene - Alcohol - > c - c c= - c + H - - x -I Hydration 20on30 & HX(Hydrohalogenation) of 30% HzSoy 1H 20 0H -> H c-c-oH - -" Hydroboration -oxidation (Syn) Oppo-Markovkin or 1) THE BIts 2) HgOz/0 HO M AIkene - Xz(Anti) x c = BzHo - S XaIHzo -c c- j CH2Is * > 68% # poxidation = - CH2C2 & c ~ O CHzCO2I7 + Rd0+ + = Ozonolysis - c-c- or H28 Xt (Anti) ↑ --OH will go for more s ubstituted Ikene-Aldehydes / Ketones / "Carboxylic & RooH CPBA Halohydoi Alcohol A (Syn ↑Peract - + ic c Xzπ -t - Alkene-Epoxides ic AKene-Alkyl Halide x x2 - =NOH Halide Alykyl now - c = of Alkenes " i 00 c 1) Os = -2) ForKUp" 6 HzOlZn Acids or = c YCI)aS Clearage of it band) (Alkynes) Ch.4 Alkyne - Bigger AlkyneSN2C-C NaNHzINHy - - - X ↑ = NaNHzINHy - . . - - Terminal - - Y ... X Alkyl Halide L x -R RN x in + Germinal 3 NaNHzINHs x - x H 20 Alkyoe Alkane - 2H2 - Y = "TMC' Alkyne --HX Alkyne Ikyne A Cis Alkene - H2 - I - Yor - i = & Lindar's Catalyst - = 2 HX I 2xzj xx ~ - xX c-c -. -- - - x2 Ikyne, Aldehydes/ Ketones ("Carboxylic - Geninal Trans Alkene Dihalide Alkyne ** A - - CiS &x here j -Tetrahaloalkanes Ozonolysis HOT (Syn) > Ketone/Aldehyde Hg Cl -E- Alkyne - Hz SOH - (Syn) Terminal i Alkyl Halides - - yX- I w .... R-E-R' Internal - vincinal * x Alkyne ↑ R'2NaNHz · Or Internal - of 1) Os 2)Hz0 Alkynes Acids ↑ - RCOH + Rort " I . x =x Ch. 10 (Free Radical AIkane Alkyl - *2 M- H U or ho AIkene (I not Halide Br R-x +Hx - picky very picky Halide JOppo-MarkouniKov Alkyl ↑ HBrg ROOR Mir Peroxide Alkyne-Trans R - C= 2 - lylic A R Allylic - R react faster H through Allylic Alkene Halide + Dienes) Carbocations Prep - [YUSTE + Hc A- c1 - Br 1 T Conjugated ↓ 1) All L Brex CHzC Diels-Alder Conjugated Dienes are preferred Resonance Forms ust be available Halide ↑ * n Minor ↑ ~ - j Kinetic "1,2- BR + Br H13M N Br Br + NBr Thermo " I,4Y N'Br Major C-C O -III Dienes from Ch.7oxns Allylic Hydrogens 2) Both Diene j SN7 must be equivalent ~ #HX N benzene Y ↓ cisdiene dienophile - c R Carbocations, Radicals, & Avions Radical W W - =C Halides also react faster SN2 212 A j NH Halides Allylic 1) H Na(Li, 12) (Allylie Ch.11 Alkere my x Stereo specific Endo Preferred k [Pry) E Ch.12 (Areres & enzylic Halides react fast than allylichalides Free Radical Bromination lkyl A Benzene uses Carboxylic ↓ NBS (see in SNE/Sr2 Ch. 11) Acid Oxidation X aacro po or 10. * 1 Vinyl 1 Kmn0+1H2018 ~ 2)H+ a Po 1 W Benzenes made from Ch.7rxns Avene Non-conjugated Diene - Birch Reduction * ↑xsaqcr6 - 1 alftsIme out => N + j 1 N I Isomers Constitutional ↓ Completely locations Stereoisomers different it ◦ ↓ × Diastercomers {H Switching Enantiomers completely changed Rls to SIR some chirality from Rts to SIR meso > Achiral but has chiral centers Plane of symmetry conformational J rotation or " cci " like process Functional Group Anatom/group responsible under for in its a reactivity given set of a ↑ c-c-alkane - -I c =c - - -C-o-H - 0 - a c ic c +) (R0 (OR) - 8 avere I - (Benzene Ring S -Q - alkyl x Ketone R (FHalosethe O aldehyde -L H R O P Carboxylic Acid - c-0H & R-% R - C OR O ~ - 0 -c- R Ester Anhydride halide (haloalkane) C - alkene = alcohol I - conditions alkyne ether - molecule 1 R - c - x acylhalide Rei Nitro -Amine