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Appendix 2 Principal Reactions of Functional Groups1 8,2 10.4.2 8.4.2 8.4.3 HO CN R OH RO OR RS SR NR 8.6.1 1) RMgX ROH 2) H3O+ H+ H H 10.2.2 o (a) (b) H NHR NaBH3CN R (a) LiAIH4 H OH 10.2.1 aldehyde (b) NaBH4 10.1.1 NR2 R2NH/H+ ketone (a) R H: Cr(VI) 8.6.2 14.4 1) H3O+ OH 17.4.2 2) acid Ph3P base OH 17.2.1 8.7 Wittig reaction 17.2.2 enol X2 17.4.1 o o RX X2 17.8 R o X 17.4.2 o o OH o OEt enolate 17.6.3 17.5 aldol reaction 1) LiAIH4 o 2) H3O+ 10.1.2 10.1.2 R OH RCH2NR'R" carboxylic acid 1) LiAIH4 R'OH 2) H3O+ H+ 1) LiAIH4 2) o o o o R'OH R'R"NH 17.6 RCOR' II NaOR' RCCI RCNR'R" R OR' Claisen (R',R" = R" 1) R"MgX alkyl,alkyl) 2) H3O+ 1) o 2) H3O+ R" 10.4.2 RCOCR R -C-OH o Chap. 9 10.4.2 R" 1 (a), (b), etc., above or under arrows indicate alternative reactions. Relevant sections are given in red.606 Appendix 2 X elimination 12.2/12.4 R-Y Chap. 13 R-X (Y = HO-, RO-, ROH, H RS-, RSH, CN-, R2NH, Mg/Et2O haloalkane R-MgX 10.4.1 HX H+ 14.1.2 R-X OH 14.1.3 R-OH o R'COY 9.5 II H H+ R'COR R-O-R 14.1.1 (Y = OH/H+, CI) alcohol RONa R'X R'SO2C1 (R = R-O-R' 12.2 14.3.1 PCC o o II II R"CH R"COH 14.4 R-NH2 R'X R'X R'X + R-N2+ R-NHR' R-NR'2 R-NR'3 X amine 14.7.2 (primary) 14.7.1 15.10 H H H o 15.2 15.5 X X HO OH X2 15.4 21.2.4 X (a) 1) OsO4, 2) H2S (b) KMnO4 H (a) H2O/H2SO4 15.3.1 alkene 15.3.2 (b) 1) Hg(OAc)2/H2O 1) O3 o + o 21.2.3 HO 2) NaBH4 2) Zn/AcOH (Markovnikov) + Y H OH X Y Z X Z 15.3.3 21.2.2 (anti-Markovnikov) 1,3-dipolar cycloaddition 15.9 Diels-Alder reaction 21.2.1Appendix 2 607 H H HX 15.10 H2 RCX2-CH3 15.2.4 cis Lindlar catalyst H R X Li R H X2 15.10 15.4 liq. NH3 H alkyne X H t-BuOH trans trans THE (a) BuLi o BH3 (b) RMgX o (c) 15.3.4 15.3.4 RCH2CH RCCH3 R'X R M+ R R' 12.2 10.4.1 16.3.3 HNO3, H2SO4 Ar - 16.3.2 RX, AIX3 16.3.4 Ar-R ( Sn/HCI Friedel- Crafts o arene Ar-NH2 16.3.5 Ar-C-R Na X2, 18.8 16.3.1 AIX3 CuX 20.9.1 H2O Ar-X Ar-X Birch Br) Ar-OH KI Br, CN) reduction 18.6 RONa Ar-H Ar-I Ar-N2+ Ar-F Ar-OR 18.8 BF4Appendix 3 Syntheses of Classes of X = CI, Br, I Type of reaction Relevant entries (1) Alkanes (R-H) Bu3SnH R-X R-H Reduction 20.4 Mg/Et2O H3O+ R-X Reduction via R-MgX R-H Grignard reagent 10.4.2 o (a) Zn(Hg), HCI H H (a) Clemmensen reaction (b) KOH (b) Wolff-Kishner reaction 10.2.2 (c) 1) HS(CH2)3SH/H+ (c) Thioacetal desulfurization 2) H2/Ni H H H H H2 ) Hydrogenation 15.10 Ni H H 2CO2 2 R -CO2 R-R Kolbe reaction 20.9.4 (anodic oxidation) (2) Alkenes (c=c) H NaOEt/EtOH Elimination 13.2 (base) Y (Y = CI, Br, I, H H2SO4/H2O (acid) Dehydration 14.1.3 OH A + NMe3 OH H H Hofmann 14.7.1 elimination A H H H Br Nal Nuleophile- Problem induced 13.16 Br elimination o R R2C=PPh3 Wittig reaction 8.7 R H H H2 Hydrogenation 15.10 Pd, CaCO3, Pb(OAc)2 (Lindlar catalyst) (cis) H NH3 Dissolving metal reduction 15.10 H (trans) 1 (a), (b), etc., above or under arrows indicate alternative reactions. Relevant sections or chapters are given in red.Appendix 3 609 (3) Alkynes X X H X X E2 elimination Chap. 13 H H H X H (strong base) M+ RCH2 reaction 12.2 (M = Li, MgX, Na) (4) Haloalkanes (R-X) X2 Radical substitution R-H R-X (low selectivity) 20.3 hv o A (a) HX (b) PX3 (or PX5) 14.1 R-OH R-X Halogenation 14.3 (c) SOX2 NaX Sulfonate R-X reaction 14.3 H HX X Electrophilic 15.2 addition X X2 X Electrophilic 15.4 addition Haloarenes (Ar-X) X2 Electrophilic aromatic Ar-H Ar - X 16.3.1 substitution AIX3 KI Ar-NH2 Ar-N2+ (X = CI, H3O+ CuX HBF4 Diazonium salt 18.8 reactions A BF4 Ar-F610 Appendix 3 (5) Alcohols (R-OH) NaOH R-X R - OH 12.2 H (a) H2O, H2SO4 Hydration OH 14.3 (Markovnikov) (b) 1) Hg(OAc)2/H2O 2) NaBH4 HO H 1) BH3/THF Hydroboration-oxidation 14.3.3 2) (anti-Markovnikov) o H (a) NaBH4/MeOH OH Hydride reduction 10.1.1 (b) 1) 2) H3O+ o H 1) OH Hydride reduction 10.1.2 Y H3O+ H (Y = OR', X, OH) o R 1) RMgX/Et2O OH Grignard reaction 10.4.2 2) H3O+ o R 1) RMgX/Et2O OH Grignard reaction 10.4.2 OR' 2) H3O+ R 3° alcohol o 1) RMgX/Et2O OH Grignard reaction 10.4.2 R 2) H3O+ HO OH (a) KMnO4/NaOH Hydroxylation 21.2.4 (b) 1) 2) H2S syn-diol OH o Epoxidation- 15.5 NaOH ring opening 14,5,2 HO anti-diol Phenols (Ar-OH) NaOH With EWGs in Ar 18.6 Ar- X - OH A or benzyne mechanism 18.7 Diazotization- 16.6.2 Ar-NH2 Ar-OH substitution 18.8 H3O+Appendix 3 611 (6) Ethers (R-O-R) NaOR' R-X R-OR' Williamson synthesis 12.2 H2SO4 2 R-OH R-O-R Acid-catalysed substitution 14.1.1 A Aromatic ethers NaOR Ar X Ar-OR - With EWGs in Ar A Epoxides o Epoxidation 15.5 X o NaOH Electrophilic addition Problem intramolecular 15.19 OH (7) Amines (R-NR2) NH3 R-NH2, R2NH, R-X 14,7 R3N, R4N+ X 1) NaN3 2) LiAIH4 12.2 R-X R-NH2 reduction Chapt. 10 3) H2O 1) NaCN 2) LiAIH4 12,2 R-X R-CH2-NH2 reduction Chapt. 10 3) H2O o 1) LiAIH4 2) H2O R-CH2-NH2 Hydride reduction 10.1.2 R NH2 o 1) Br2/NaOH 2) H2O - Hofmann rearrangement 22.5.2 R NH2 o H RNH2/NaBH3CN NHR Reductive amination 10.2.1 Arylamines (Ar-NH2) Sn/HCI Ar-NH2 Reduction 16.6 Ar-X Ar-NH2 Benzyne mechanism 18.7612 Appendix 3 (8) Nitriles (R-CN) NaCN R-X R-CN reaction 12.2 o Il NaCN/H3O+ HO CN Cyanohydrin formation 8.2 1) H3O+ Ar-NH2 Ar-CN Sandmeyer reaction 18.8 2) CuCN o (9) Aldehydes (R-C-H) OH + (a) NH o (a) PCC oxidation R-CH2 (b) R H (b) Swern oxidation o o 1) DIBAL 2)H3O+ Reduction 10.1.2 R Y R H NMe2) [DIBAL = o o 1) RMgX/Et2O Grignard reaction 10.4.2 H NMe2 2) H3O+ R H H o 1) O3 2) Zn/AcOH 2 Ozonolysis- 21.2.3 reductive workup H H o 1) BH3/THF Hydroboration- R H oxidation 15.3.4 2) RCH2 HAppendix 3 613 o (10) Ketones (R-C-R) H OH o Oxidation 14.4 R R' H2SO4/H2O R R' o R'MgX/Et2O Grignard reaction 10.4.2 R NMe2 2) H3O+ R R' o 2) Zn/AcOH Ozonolysis- 2 21.2.3 reductive workup o R H Oxymercuration 15.3.4 R CH3 o o o 1) NaOEt/EtOH R-X + CH3 OEt 2) H3O+ CH3 CH2R Acetoacetate synthesis 17.8.2 o o Ar- H Friedel-Crafts acylation Ar R o (11) Carboxylic acids (R-COH) OH o o Oxidation 14.4 R H H2SO4/H2O R OH Mg/Et2O R-X R-CO2H Grignard reaction 10.4.2 (a) NaOH/H2O R-CN R-CO2H Hydrolysis Chapt. 9 (b) H2SO4/H2O o o 1) Haloform reaction 17.4.2 R CH3 R OH o o 1) NaOEt/EtOH EtO R -CH2CO2H Malonate synthesis 17.8.2 OEt 3) (a) 1) Ar-CHR2 Ar-CO2H Oxidation (b)614 Appendix 3 o (12) Carboxylic acid derivatives (R-C-Y) o o SOCI2 Halogenation 9.5.1 R OH R CI o o R'OH/H2SO4 Fischer esterification R OH R OR' o o YH Substitution 9.5.1 R CI R Y (Y = R'COO, R'O, o o RCO3H Baeyer-Villiger 22.4.1 R R' R OR' oxidation NOH o H2SO4 Beckmann 22.4.2 R R' R' NHR rearrangement