CHEM 238 Organic Chemistry
Contents
Ch10 Alcohol, Thiol Reactions
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Dehydration of alcohol | alcohol | phosphoric acid H3PO4 | alkene, water | $\ce{ROH ->[H3PO4] alkene + H2O}$ |
| Alcohol and HX | alcohol, hydrogen halide | alkyl halide, water | $\ce{ROH + HX -> RX + H2O}$ | |
| Alcohol and sulfonate ester TsCl | alcohol, sulfonate ester TsCl, ROTs | pyridine, NaBr | alkyl bromide | $\ce{ROH + TsCl ->[pyridine] R-OTs ->[NaBr] RBr}$ |
| Alkoxide and inorganic acid | alkoxide, inorganic acid (dimethyl sulfate) | ester, conjugate base | $\ce{RO- + (CH3)2SO4 -> ROCH3 + CH3SO4-}$ | |
| Alcohol and SOCl2 | alcohol, thionyl chloride SOCl2 | pyridine | alkyl chloride, sulfate dioxide, hydrogen chloride | $\ce{ROH + SOCl2 ->[][pyridine]RCl + SO2 + HCl}$ |
| Alcohol and Ph3PBr2 | alcohol, triphenylphosphine dibromine Ph3PBr2 | DMF | alkyl bromide, base | $\ce{ROH + Ph3PBr2 ->[][DMF] RBr + Ph3P+O- + HBr}$ |
| Oxidation of secondary 2nd alcohol | secondary alcohol, Cr(VI) (PCC) | ketone, Cr(III) | $\ce{ROH + Cr(VI) (CrO3, pyridine) -> R=O + Cr(III)}$ | |
| Oxidation of primary 1st alcohol | primary alcohol | Cr2O4- | aldehyde, carboxylic acid | $\ce{RCH2OH ->[Cr2O4-][H2SO4] RCH=O ->[Cr2O4-][H2SO4] RC-OH=O}$ |
| Controlled oxidation of primary 1st alcohol | primary alcohol | PCC | aldehyde | $\ce{RCH2OH ->[PCC][CH2Cl2] RCH=O}$ |
| Oxidation of primary alcohol | primary alcohol, potassium permaganate KMnO4 | carboxylic acid’s conjugate base | $\ce{RCH2OH + KMnO4 + OH- -> MnO2 + RCOO- ->[H3O+] RCOOH}$ | |
| Oxidation of thiols/disulfide | thiols/disulfide, KMnO4/HNO3 | sulfonic acid | $\ce{RSH ->[HNO3] RSO3H}$ | |
| Oxidation of thiols | thiol, oxygen O2/iodine I2/bromine Br2 | disulfide | $\ce{2RSH + I2 + 2NaOH -> RSSR + 2NaI + 2H2O}$ |
Synthesis of alcohol
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Hydroboration-oxidation | alkene | HBR2, H2O2/OH- | alcohol | $\ce{alkene ->[(1) HBR2][(2) H2O2/OH-] ROH}$ |
| Oxymercuration-reduction | alkene | Hg(OAc)2/H2O, NaBH2/NaOH | alcohol | $\ce{alkene ->[(1) Hg(OAc)2/H2O][(2) NaBH2/NaOH] ROH}$ |
| Acid-cayalyzed hydration of alkene | alkene, water H2O | acid | alcohol | $\ce{alkene + H2O ->[H3O+] ROH}$ |
Ch11 Ether, Sulfide, Epoxide, Glycol
Synthesis, Cleavage of ether
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Williamson ether synthesis | alcohol | NaH, THF | ether | $\ce{ROH ->[NaH][THF] RO- + Na+ + H2 ->[XR'] ROR' + NaX + H2}$ |
| Williamson sulfide synthesis | thiol | ROTs | sulfide | $\ce{RSH ->[OH-][CH3OH] RS- + H2O ->[R’OTs] RSR' + H2O + OTs-}$ |
| Alkoxymercuration-reduction | alkene | Hg(OAc)2/HOR, NaBH4 | ether | $\ce{alkene ->[(1) Hg(OAc)2/HOR'][(2) NaBH4] -> ROR'}$ |
| Primary 1st alcohol dehydration | primary alcohol | sulfuric acid H2SO4, heat | ether, water H2O | $\ce{2ROH ->[H2SO4, \Delta] ROR + H2O}$ |
| Tertiary 3rd alcohol dehydration | tertiary alcohol, primary alcohol | sulfuric acid H2SO4 | ester, water H2O | $\ce{ROH + R’OH ->[dilute H2SO4] ROR' + H2O}$ |
| Alkene addition by tertiary alcohol | alkene, tertiary alcohol | sulfuric acid H2SO4 | ether | $\ce{alkene + ROH ->[dilute H2SO4] (CH3)3COR;}$ |
| Ether cleavage | ether, hydrogen halide | heat | alcohol, alkyl halide | $\ce{ROR' + HX ->[\Delta] ROH + R’X}$ |
Synthesis of epoxide
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Oxidation of alkene with RCOOOH | alkene, peroxycarboxylic acid RCOOOH (MCPBA) | epoxide, carboxylic acid | $\ce{alkene + RCOOOH (MCPBA) -> epoxide + RCOOH}$ | |
| Cyclization of halohydrin | halohydrin (alcohol + alkyl halide RX), base | epoxide, water H2O | $\ce{halohydrin (OH-C-C-X) + NaOH -> epoxide + NaX + H2O}$ |
Ring opening of epoxide
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Base ring opening | epoxide, alcohol | alkoxide | alcohol-ether | $\ce{epoxide + R’OH ->[R’O-] ester-alcohol}$ |
| Acid ring opening | epoxide, alcohol | acid | alcohol-ether | $\ce{epoxide, R’OH ->[H3O+] alcohol-ether}$ |
| Grignard organometallic ring opening | Grignard reagent MgBr, epoxide | ether, heat, acid H3O+ | alcohol | $\ce{epoxide + R’MgBr ->[(1) ether, heat][H3O+] R’CR2CR2OH}$ |
Preparation, Cleavage of glycol
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Acid ring opening (hydrolysis) of epoxide | epoxide, water H2O | acid | glycol | $\ce{epoxide + H2O ->[acid] glycol}$ |
| Oxidation of alkene by OsO4 | alkene, osmium tetroxide OsO4 | water H2O, NaHSO3 | glycol | $\ce{R2C=CR2 + OsO4 ->[H2O][NaHSO3] glycol + OsO3(OH)2}$ |
| Alkene + KMnO4 | alkene, potassium permanganate KMnO4 | water, acetone | glycol, MnO2 | $\ce{alkene + KMnO4 ->[H2O, OH-][acetone] glycol + MnO2}$ |
| Glycol cleavage | glycol, periodic acid H5IO6 | HOAc | aldehyde, ketone, water | $\ce{glycol + H5IO6 ->[HOAc] R'-CH=O + R-CR=O + 2H2O + HIO3H2O}$ |
Oxonium salt
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Oxonium salt | nucleophile, oxonium salt | alcohol | $\ce{Nu- + R3O+ -> ROH + H2O}$ |
Ch14 Alkyne Reactions
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Alkyne addition | alkyne, hydrogen halide | alkene halide | $\ce{C#C + HX -> XC=C}$ | |
| Hydration of alkyne | alkyne, water | mercury ion, sulfuric acid H2SO4 | ketone | $\ce{RC#CH + H2O ->[Hg^2+, H2SO4] RC=OCH3}$ |
| Hydroboration-oxidation of symmetric alkyne | symmetric alkyne | borane BH3, THF, hydrogen peroxide | ketone | $\ce{R-C#C-R ->[(1) BH3/THF][(2) H2O2/OH-] R-CH2-C=O-R}$ |
| Hydroboration-oxidation of asymmetric alkyne | asymmetric 1-alkyne | disiamylborane, THF, hydrogen peroxide | aldehyde | $\ce{R-C#C-H ->[(1) (branch)2BH/THF][(2) H2O2/OH-] R-CH2-C=O-H}$ |
| Catalytic hydrogenation of alkyne | alkyne | hydrogen gas H2, catalyst | cis alkene | $\ce{RC=CR ->[H2, catalyst] RCH=HCR}$ |
| Catalytic hydrogenation of alkene | alkene | hydrogen gas H2, catalyst | alkane | $\ce{RCH=HCR ->[H2, catalyst] RCH2=H2CR}$ |
| Controlled catalytic hydrogenation of alkyne | alkyne | Lindlar catalyst/(Pd/C), pyridine | cis alkene | $\ce{RC=CR ->[Lindlar catalyst Pd/CaCO3 + Pb(OAc)2][or Pd/C, pyridine] RCH=HCR}$ |
| Reduction of alkyne with Na and NH3 | alkyne, sodium, liquid ammonia | trans alkene, sodium ion, azanide | $\ce{RC=CR + 2Na + 2NH3 -> RCH=HCR + 2Na+ + 2NH2-}$ | |
| Grignard reaction of alkyne | 1-alkyne, Grignard reagent | THF | acetylenic Grignard reagent, hydrocarbon | $\ce{RC#CR + R’MgBr ->[THF] RC#CMgBr + R'}$ |
| Alkyne in SN2 rxn | alkane halide, acetylenic anion | alkyne, halide ion | $\ce{RX + C#CR- -> RC#CR + X-}$ |
Ch15 Diene Reactions
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Diels-Alder Rxn | diene, alkene (dienophile) | ring | $\ce{diene + dienophile -> ring}$ | |
| Addition of HX to conjugated diene | conjugated diene, hydrogen halide | alkene halide | $\ce{conj. diene + HX -> mixed alkene halide}$ |
Ch16 Benzene Reactions
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Halogenation of benzene | benzene, halide gas X2 | iron/iron(iii) bromide FeBr3 | benzene halide, hydrogen halide | $\ce{Ph + X2 ->[FeBr3/Fe] PhX + HX}$ |
| Nitration of benzene | benzene, nitric acid HNO3 | sulfuric acid H2SO4 | nitrobenzene, water | $\ce{Ph + HNO3 ->[H2SO4] PhNO2 + H2O}$ |
| Sulfonation of benzene | benzene, sulfur trioxide | fuming sulfuric acid H2SO4 | benzenesulfuric acid | $\ce{Ph + SO3 ->[fuming H2SO4] PhSO3H}$ |
| Friedel-Crafts alkylation of benzene | benzene, alkyl chloride | aluminum chloride AlCl3 | alkyl benzene, hydrogen chloride | $\ce{Ph + RCl ->[AlCl3] PhR + HCl}$ |
| Friedel-Crafts acylation of benzene | benzene, acyl chloride | aluminum chloride AlCl3, water | ketone, hydrogen chloride | $\ce{Ph + Cl-CR=O ->[(1) AlCl3][(2)H2)] Ph-C=OCH3 + HCl}$ |
| Hydrogenation of benzene | benzene, hydrogen gas H2 | Ni | cyclohexane | $\ce{Ph + 3H2 ->[Ni][175^oC, 180atm] cyclohexane}$ |
| Hydrogenation of benzene derivatives | benzene derivative, hydrogen gas H2 | Ni | substituted cyclohexane | $\ce{PhR + 3H2 ->[Ni][175^oC, 180atm] cyclohexane-R}$ |
Ch17 Allylic/Benzylic Reactions
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Radical bromonation of allylic/benzylic hydrogen | allylic/benzylic species, bromine gas Br2 | light hv | allylic/benzylic bromide, hydrogen bromide | $\ce{PhCH3 + Br2 ->[light hv] PhCH2Br + HBr} \newline \ce{CH3-CH2=CH2 ->[light hv] BrCH2-CH2=CH2}$ |
| Controlled radical bromonation of allylic/benzylic hydrogen | allylic/benzylic species, NBS (N-bromosuccinimide) | heat/light, peroxide | allylic/benzylic bromide, succinimide | $\ce{PhCH3 + NBS ->[heat/light, peroxide][CCl4] PhCH2Br} \newline \ce{CH3-CH2=CH2 + NBS ->[light hv] BrCH2-CH2=CH2 + succinimide}$ |
| Allylic/benzylic Grignard Reagent | alkene bromide Br, magnesium Mg | alkene, MgBrOH | $\ce{-> see Ch 17 allylic Grignard reagent}$ | |
| Allylic/benzylic E2 elimination | allylic/benzylic bromide | EtOH, Na+, EtO- | alkene | $\ce{Ph-CH2CH2-Br ->[Na+, EtO-][EtOH] Ph-CH2CH2-OEt}$ |
| Oxidation of allylic/benzylic alcohol with MnO2 | allylic/benzylic alcohol, manganese dioxide MnO2 | CH2Cl2 | aldehyde/ketone, Mn(OH)2 | $\ce{PhCH2OH + MnO2 ->[][CH2Cl2] PhCH=O + Mn(OH)2} \newline \ce{H2C=CH-CH2OH + MnO2 ->[][CH2Cl2] H2C=CH-CH2=O + Mn(OH)2}$ |
| Benzylic oxidation of alkylbenzene | alkylbenzene | Cr(VI): Na2CrO7/CrO3; Mn(VII): KMnO4; O2 + catalyst | benzylic carboxylic acid | $\ce{PhR ->[Na2CrO7/CrO3][or KMnO4 or O2 + catalyst] PhCOOH}$ |
| Biosynthesis of terpene | isopentenyl pyrophosphate IPP, gamma,gamma-dimethylallyl pyrophosphate DMAP | prenyl transferase | terpene, HOPP | $\ce{IPP + DMAP ->[prenyl transferase SN1] terpene, HOPP}$ |
Ch18 Vinylic/Aryl Halide Reactions
| Reaction | Reactant | Condition | Product | Overall |
|---|---|---|---|---|
| Vinylic/aryl halide under SN1, SN2 conditions | Vinylic/aryl halide | SN1, SN2 | no reaction | $\ce{CH2=CHX + Nu ->[SN1, SN2] no reaction} \newline \ce{PhX + Nu ->[SN1, SN2] no reaction}$ |
| Elimination of vinylic halide | vinylic halide, nucleophile (hydroxide) | harsh conditions, high temp | vinylic alkyne, bromide, water | $\ce{Ph-CH=CH-Br + KOH ->[][200^{\circ}C] Ph-C#C-H + KBr + H2O}$ |
| Nucleophilic aromatic substitution of aryl halide | nitro aryl halide, nucleophile | nitro aryl nucleophile: halide ion | $\ce{O2N-Ph-X + Nu- -> O2N-Ph-Nu + X-}$ | |
| Heck reaction (aryl) | aryl bromide/iodide, alkene | Pd(0) catalyst (Pd(OAc)2, Pd(PPh3)4) | aryl alkene, hydrogen bromide | $\ce{PhBr + alkene ->[Pd(0)] Ph-alkene + HBr}$ |
| Heck reaction (general) | alkyl halide + alkene | Pd(0) catalyst (Pd(OAc)2, Pd(PPh3)4) | alkene, hydrogen bromide | $\ce{R1X + alkene-R2 ->[PdL4] R1-alkene-R2 + HX}$ |
| Suzuki coupling | aryl boronic acid, aryl halide, sodium hydroxide | Pd(OAc)2, PPh3, Na2CO3 | biaryl compound, NaBr, B(OH)2 | $\ce{RB(OH)2 + R’X + NaOH ->[Pd(OAc)2, PPh3, Na2CO3] RR' + NaBr + B(OH)2}$ |
| Oxidation of phenol | phenol -> semiquinone | Na2Cr2O7, H2SO4 | quinone | $\ce{Ph(OH)2 ->[Na2Cr2O7, H2SO4] quinone}$ |
| Bromination of phenol | phenol, bromine gas | CCl4, Hbr, water H2O | phenol bromide | $\ce{PhOH + nBr2 ->[various conditions] PhOH-Br_n + nHBr}$ |
| Nitration of phenol | phenol | nitric acid HNO3 | nitric phenol | $\ce{PhOH ->[HNO3] PhOH-NO2 + H2O}$ |
| Friedel-Crafts alkylation | phenol, alcohol | sulfuric acid H2SO4 | alkyl phenol, water H2O | $\ce{PhOH + ROH ->[H2SO4] RPhOH + H2O}$ |
| Friedel-Crafts acylation | phenol, AlCl3, acyl chloride | PhNO2 | acyl phenol | $\ce{PhOH + AlCl3 + RC=O-Cl ->[PhNO2] PhOH-CR=O}$ |