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Summary of Reactions Which Will Appear on Exams 1. COMBUSTION OF HYDROCARBONS (ALKANES/ALKENES/ALKYNES, etc) CxHy + (x + y/4)O2 xCO2 + y/2H2O + heat C10H20 + 15O2 10CO2 + 10H2O (this is the only reaction you will need to balance; for all others only the organic product(s) required) 2. FREE RADICAL HALOGENATION OF ALKANES light or heat R-X + H-X R-H + X-X X = Cl, Br light CH3-Cl + H-Cl CH4 + Cl2 heat CH3-CH3 + Br2 CH3-CH2-Br + H-Br (you need to know the mechanism) 3. HYDROGENATION OF ALKENES H H C C R R' CH3 CH3 metal catalyst (Ni, Pt or Pd) H2 metal catalyst (Ni, Pt, Pd) H H H C C R H R' H H CH3 H2 CH3 cis product syn-addition of hydrogen 4. ADDITION OF HX TO ALKENES H R" C H H-X C R R' H X C C R" R R' X = Cl, Br, I X = OH, H2SO4 catalyst required (hydration) Markovnikov addition (you need to know the mechanism) 5. ADDITION OF X2 TO ALKENES H H C H X-X C R R' X X C C R H R' X = Cl, Br X CH3 CH3 X-X anti-addition of halogen X CH3 CH3 trans product 6. DIHYDROXYLATION OF ALKENES H H C C R KMnO4 cold, NaOH R' CH3 KMnO4 cold, NaOH/H2O H OH OH C C R R' OH OH CH3 CH3 H CH3 cis product syn-addition of OH groups 7. OXIDATIVE CLEAVAGE OF ALKENES H R" C C R KMnO4 in H2O, H+ H R" C R' + O O C R R' a ketone an aldehyde further oxidation HO C R O a carboxylic acid 8. FREE RADICAL POLYMERIZATION OF ALKENES CH2=CH heat R'O-(CH2-CH)-(CH2-CH)n-etc + R'O-OR' R R R (you need to know the mechanism--in packet) 9. HYDROGENATION OF ALKYNES R C C metal catalyst (Ni, Pt or Pd) H 1H2 R H C R' syn addition C R' cis product 10. HALOGENATION OF ALKYNES X2 R C C R C R' X X = Cl, Br X anti addition C R' trans product 11. HX ADDITION TO ALKYNES R H-X R C C H C H C X X = Cl, Br, I (you need to know the mechanism) H Markovnikov addition 12. HYDRATION OF ALKYNES R H2O R C C H H C H2SO4 HgSO4 catalysts R CH3 C C HO H O an enol (unstable) a ketone Markovnikov addition 13. ALKYLATION OF TERMINAL ALKYNES _ NaNH2 R C C R H C C Na+ + R'CH2X R C C CH2R' or (or CH3X) (X=Cl, Br, I) (2o or 3o alkyl halides do not work) (R C 14. HALOGENATION OF CONJUGATED DIENES 1 2 3 4 CH2=CH-CH=CH2 X2 1 2 3 4 1 2 3 4 CH2-CH-CH=CH2 + CH2-CH=CH-CH2 X X = Cl, Br X X X 1,4-addition 1,2-addition 15. HX ADDITION TO CONJUGATED DIENES 1 2 3 4 CH2=CH-CH=CH2 H-X 1 3 4 1 2 3 4 CH2-CH-CH=CH2 + CH2-CH=CH-CH2 H X = Cl, Br 2 X 1,2-addition H X 1,4-addition C CH3) 16. ELECTROPHILIC AROMATIC SUBSTITUTION E reagents X X halogenation Cl2/FeCl3 or AlCl3 (cat) E = Cl Br2/FeBr3 or AlBr3 (cat) E = Br nitration HONO2/H2SO4(cat) E = NO2 sulfonation HOSO3H E = SO3H Friedel-Crafts alkylation R-Cl/AlCl3 (cat) E=R O Friedel-Crafts acylation R O C Cl /AlCl3 (cat) E = C-R (you need to know the mechanism and the directing effects of various substituents "X") 17. AROMATIC SIDECHAIN OXIDATION TO BENZOIC ACIDS CH-R X R' KMnO4 H2O, heat CO2H X R, R' = alkyl or H 18. AROMATIC RING REDUCTION TO CYCLOHEXANES R 3H2 Pt cat high pressure R 19. REDUCTION OF NITRO GROUPS TO ANILINES NO2 NH2 Fe HCl X X 20. CONVERSION OF SULFONIC ACIDS TO PHENOLS SO3H OH NaOH 300 oC X X + then H3O 21. REDUCTION OF CARBONYL COMPOUNDS TO ALCOHOLS NaBH4 ethanol O C R H aldehydes O or LiAlH4, ether; then H3O+ primary alcohol OH NaBH4 ethanol C R R-CH2OH R' ketones O LiAlH4, ether; then H3O+ C R OR' esters or LiAlH4, ether; then H3O+ C R R' H secondary alcohol R-CH2OH + R'OH primary alcohol (you need to know the mechanism of aldehyde and ketone reductions but not esters) 22. OXIDATION OF ALCOHOLS TO CARBONYL COMPOUNDS O R-CH2OH CrO3 or Na2Cr2O7 C R R-CH2OH primary alcohol (PCC = pyridinium chlorochromate) H aldehyde O CrO3 or Na2Cr2O7 C R' R H CrO3 or Na2Cr2O7 C R R' ketone secondary alcohol OH OH carboxylic acid C R C R O PCC R C H aldehyde primary alcohol OH O R' no reaction R" tertiary alcohol (You need to know the mechanism of oxidation of alcohols to aldehydes and ketones with CrO3) 23. CONVERSION OF ALCOHOLS TO ALKYL HALIDES R-OH R-OH SOCl2 PBr3 R-Cl R-Br 24. WILLIAMSON ETHER SYNTHESIS R-O-CH2R' R'CH2-X Na or NaH _ R-O R-OH Na+ + or R-O-CH3 CH3-X X = Cl, Br, I (2o or 3o alkyl halides usually do not work in this reaction) 25. POLYMERIZATION OF EPOXIDES base cat (B) O H2C CH R R B-(CH2-CH-O)n-CH2-CH-O-etc R (you need to know the mechanism--in packet) 26. ACID/BASE REACTIONS OF CARBOXYLIC ACIDS, PHENOLS AND AMINES NaHCO3 or NaOH O O C C R OH HCl or H2SO4 R O- Na+ NaOH (but not NaHCO3) ArO- Na+ Ar-OH HCl or H2SO4 HCl R3NH+ Cl- R3N NaOH 27. ALKYLATION OF AMINES N •• R' R'''CH2X R R' R + N X+ R" or R R" CH3X (1o, 2o or 3o) R, R', R" = alkyl, H, aryl CH2R''' R' X = Cl, Br, I N X+ CH3 R" a quaternary ammonium salt (2o or 3o alkyl halides usually do not work in this reaction) Ph H Ph CH3CH2I N •• H CH3 N + Ph INaOH •• N CH2CH3 CH3 a quaternary ammonium salt (only if there is at least one H on the nitrogen) CH2CH3 CH3 28. SYNTHESIS OF GRIGNARD REAGENTS AND ORGANOLITHIUM COMPOUNDS ether R-X + R-Mg-X Mg Grignard reagent R-X + 2Li alkane solvent X = Cl, Br, I R-Li + LiX 29. REACTIONS OF GRIGNARD REAGENTS AND ORGANOLITHIUM COMPOUNDS R-Mg-X H2O or R-H R-Li O R-Mg-X CO2 R-COH or then H3O+ R-Li R O R-Mg-X then H3O C R'CH R' aldehyde R-Li O R-Mg-X + or H 2o alcohol R then H3O+ OH C R'CR" R' ketone R-Li OH + + or a carboxylic acid R" 3o alcohol (you need to know the mechanism--in packet) 30. ELIMINATION OF ALKYL HALIDES TO ALKENES H X C H H R H NaOH C C R' R H X = Cl, Br, I (you need to know the mechanism) C + NaX R' 31. HYDRATION OF ALDEHYDES AND KETONES H2O acid or base catalyst O HO OH C RCH R' H HO OH aldehyde O H2O acid or base catalyst C R'CR R' ketone R (you need to know the mechanism--in packet) 32. REACTIONS OF ALDEHYDES AND KETONES WITH ALCOHOLS O R"OH base catalyst RCH HO OR" C R' H HO OR" a hemiacetal aldehyde O R"OH base catalyst C R'CR ketone O 2R"OH acid catalyst RCH a hemiketal R' R R"O OR" C R' H an acetal aldehyde O 2R"OH acid catalyst R"O C R'CR ketone OR" R' a ketal R (you need to know the mechanism--in packet) 33. CYANOHYDRINS FROM ALDEHYDES AND KETONES O HO HCN NaCN CN C RCH R' H HO CN aldehyde O HCN NaCN R'CR C R' ketone R (you need to know the mechanism--in packet) 34. REACTIONS OF ALDEHYDES AND KETONES WITH AMINES AND DERIVATIVES O + C R NZ H+ cat Z-NH2 C R H H aldehyde O + C R NZ + H cat Z-NH2 C R R' R' ketone Z = OH, NHPh, alkyl, aryl (you need to know the mechanism--in packet) 35. OXIDATION OF ALDEHYDES TO CARBOXYLIC ACIDS Ag+1 NH4OH O O C R C H O R OH O Cu+2 C R (Tollens oxidation) Fehling or Benedict oxidation C H R OH 36. SYNTHESIS OF CARBOXYLIC ACID CHLORIDES AND ANHYDRIDES O O + C R SOCl2 C OH R Cl O O 2 + C R O C SOCl2 R OH C O R 37. HYDROLYSIS OF CARBOXYLIC ACID CHLORIDES AND ANHYDRIDES O O H2O C + HCl C R Cl R O O C C R O OH O H2O 2 C R R OH 38. REACTION OF CARBOXYLIC ACID CHLORIDES AND ANHYDRIDES WITH ALCOHOLS O O R'OH C R + HCl C Cl R OR' an ester O C R O O R'OH + C C O O R R OR' C R OH 39. FISCHER ESTERIFICATION OF CARBOXYLIC ACIDS TO ESTERS O O + + C R H cat R'OH + H2O C R OH OR' (must remove water) an ester (you need to know the mechanism) 40. HYDROLYSIS OF ESTERS TO CARBOXYLIC ACIDS AND ALCOHOLS O O + H cat + H2O C R R + C R OR' O O C C + NaOH R'OH + OH O HCl _ O Na R OR' R'OH + R (you need to know the mechanisms for both of these) 41. AMINOLYSIS OF ESTERS TO AMIDES O O heat + HNR"2 C R R OR' R" = H, alkyl, aryl + C NR"2 an amide C R'OH OH 42. REACTIONS OF GRIGNARD REAGENTS AND ORGANOLITHIUM COMPOUNDS WITH ESTERS TO FORM TERTIARY ALCOHOLS 2 R"-Mg-X O + or C R OH then H3O+ R 2 R"-Li OR' + C R'-OH R" R" (you need to know the mechanism) 43. REACTION OF CARBOXYLIC ACID CHLORIDES AND ANHYDRIDES WITH AMINES O O C R + HNR'2 Cl C R NR'2 an amide O O C C R O O + HNR'2 O + C R R NR'2 R' = H, alkyl, aryl 44. HYDROLYSIS OF AMIDES HCl H2O heat O O C R NR'2 R NaOH H2O heat O OH O C R + HNR'2 C C NR'2 R _ O (you need to know the mechanism) + HNR'2 + Na C R OH