Contents

CHEM 238 Organic Chemistry

2021-08-17

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	$\ce{PhOH + AlCl3 + RC=O-Cl ->[PhNO2] PhOH-CR=O}$