Organic Chemistry Flashcards

Vocabulary flashcards for reviewing organic chemistry reactions.

Carbocation Rearrangement

Yields a more stable carbocation through the shift of a hydrogen atom or an alkyl group.

R-X + OH-

Yields an alcohol (R-OH) via SN2 mechanism, best for CH_3X and 1° RX.

R-OH + NaH

Yields an alkoxide (R-O-Na+) and hydrogen gas (H_2) through a Brønsted-Lowry acid-base reaction.

R-X + OR'

Yields an ether (R-OR') and a halide ion (X-) via SN2 mechanism, best for CH_3X and 1° RX.

Halohydrin + Base

Yields an epoxide through proton removal and intramolecular SN2.

Alcohol + H2SO4 or TsOH

Yields an alkene and water through dehydration, following Zaitsev's rule with possible carbocation rearrangements.

Alcohol + POCl_3/pyridine

Yields an alkene and water through E2 dehydration, without carbocation rearrangements.

R-OH + H-X

Yields an alkyl halide (R-X) and water with reactivity order R3COH > R2CHOH > RCH2OH; 2° and 3° ROH proceed via E1/SN1, 1° ROH via E2/SN2.

R-OH + SOCl2/pyridine or PBr3

Yields R-Cl with SOCl2/pyridine or R-Br with PBr3 via SN2 for CH_3OH, 1°, and 2° ROH.

R-OH + TsCl/pyridine

Yields an alkyl tosylate (R-OTs) with retained configuration at stereogenic center.

R-OTs + Nu-

Yields substitution or elimination products; SN2 favored by strong nucleophiles, E2 by strong bases; SN1 favored by 2° and 3° R groups, SN2 by CH_3 and 1° R groups.

R-O-R' + HX (2 equiv)

Yields two alkyl halides (R-X and R'-X) and water through ether cleavage.

R-X + -SH

Yields a thiol (R-SH) and a halide ion (X-) via SN2, best for CH_3X and 1° RX.

2 R-SH + Br2 or I2

Yields a disulfide (R-S-S-R) through oxidation; reduction with Zn/HCl regenerates thiols.

R-X + -SR'

Yields a sulfide (R-SR') and a halide ion (X-) via SN2, best for CH_3X and 1° RX.

R'_2S + R-X

Yields a sulfonium ion (R'2S^+-R) and a halide ion (X-) via SN2, best for CH3X and 1° RX.

Epoxide + Nu-

Yields a product with backside attack and trans/anti stereochemistry via SN2, with Nu- attacking at the less substituted carbon.

Epoxide + HZ

Yields a product with Z attacking at the more substituted carbon via a mechanism between SN1 and SN2.

Alkene + H-X

Yields an alkyl halide via a two-step mechanism with a carbocation intermediate, following Markovnikov's rule with syn and anti addition.

Alkene + H-OH/H2SO4 or H-OR/H2SO4

Yields an alcohol with H2O/H2SO4 or an ether with H-OR/H2SO_4 via a three-step mechanism with a carbocation intermediate, following Markovnikov's rule with syn and anti addition.

Alkene + X-X

Yields a vicinal dihalide via a two-step mechanism with a bridged halonium ion intermediate, without rearrangements and with anti addition.

Alkene + X-X/H_2O

Yields a halohydrin via a three-step mechanism with a bridged halonium ion intermediate, without rearrangements, X bonding to the less substituted C, and anti addition.

Alkene + [1] BH3 or 9-BBN; [2] H2O_2, HO-

Yields an alcohol via a one-step mechanism, without rearrangements, OH bonding to the less substituted C, and syn addition of H_2O.

Alkyne + HX (2 equiv)

Yields a geminal dihalide, following Markovnikov's rule where H bonds to the less substituted C for carbocation stability.

Alkyne + X_2 (2 equiv)

Yields a tetrahalide through anti addition of X_2.

Alkyne + H2O/H2SO4, HgSO4

Yields an enol that rearranges to a ketone, following Markovnikov's rule with H bonding to the less substituted C.

Alkyne + [1] R2BH; [2] H2O_2, HO-

Yields an enol that rearranges to an aldehyde, with the unstable enol rearranging to a carbonyl group.

Terminal Alkyne + Base

Yields an acetylide anion and HB+, using bases like NaNH_2, NaH.

Acetylide Anion + R-X

Yields an alkyne and X- via SN2, best with CH3X and RCH2X.

Acetylide Anion + [1] Epoxide; [2] H_2O

Yields an alcohol via SN2, with ring opening from the backside at the less substituted end.

Alkene + H_2/Pd, Pt, or Ni

Yields an alkane through syn addition of H_2, with rate decreasing as alkyl substitution increases.

Alkyne + 2 H_2/Pd-C

Yields an alkane with two equivalents of H_2 added, forming four new C-H bonds.

Alkyne + H_2/Lindlar catalyst

Yields a cis-alkene through syn addition of H2, stopping after one equivalent of H2.

Alkyne + Na/NH_3

Yields a trans-alkene through anti addition of H.

R-X + [1] LiAlH4; [2] H2O

Yields R-H via SN2, with CH3X and RCH2X reacting faster than more substituted RX.

Epoxide + [1] LiAlH4; [2] H2O

Yields an alcohol via SN2, with H attacking the less substituted carbon in unsymmetrical epoxides.

Alkene + RCO_3H

Yields an epoxide via a one-step mechanism, with syn addition of O atom and stereospecificity.

Alkene + [1] RCO3H; [2] H2O (H^+ or HO-)

Yields a 1,2-diol via ring opening of epoxide intermediate, with anti addition of OH groups.

Alkene + [1] OsO4; [2] NaHSO3, H2O or [1] OsO4, NMO; [2] NaHSO3, H2O or KMnO4, H2O, HO-

Yields a 1,2-diol through syn addition, forming two new C-O bonds to C=C.

Alkene + [1] O3; [2] Zn, H2O or CH3SCH3

Yields a ketone and an aldehyde through cleavage of sigma and pi bonds.

Internal Alkyne + [1] O3; [2] H2O or Terminal Alkyne + [1] O3; [2] H2O

Yields 2 carboxylic acids from internal alkynes or a carboxylic acid and CO_2 from terminal alkynes through sigma and pi bond cleavage.

1° Alcohol + PCC

Yields an aldehyde through oxidation, with only one C-H bond replaced by a C-O bond.

1° Alcohol + CrO3/H2SO4, H2O

Yields a carboxylic acid through oxidation, with two C-H bonds replaced by two C-O bonds.

2° Alcohol + PCC or CrO_3

Yields a ketone through oxidation by all Cr^{6+} reagents.

Allylic Alcohol + (CH3)3C-OOH/Ti[OCH(CH3)2]_4 with (-)-DET or (+)-DET

Yields a chiral epoxide using chiral catalysts for specific enantiomers in Sharpless epoxidation.

Aldehyde/Ketone + NaBH4, CH3OH or [1] LiAlH4; [2] H2O or H_2, Pd-C

Yields a 1° or 2° alcohol through reduction.

α,β-Unsaturated Aldehyde/Ketone+ NaBH4/CH3OH or +H2 (1 equiv)/Pd-C or +H2 (excess)/Pd-C

Yields a product with C=O reduction only, C=C reduction only, or both pi bonds reduction.

Ketone + 1 or (R)-CBS reagent; [2] H_2O

Yields a (R) or (S) 2° alcohol, with a single enantiomer formed through CBS reduction.

Acid Chloride + [1] LiAlH4; [2] H2O or Acid Chloride + [1] LiAlH[OC(CH3)3]3; [2] H2O

Yields a 1° alcohol with LiAlH4 or an aldehyde with LiAlH[OC(CH3)3]3.

Aldehyde + CrO3, Na2Cr2O7, K2Cr2O7, KMnO4 or Ag2O, NH4OH

Yields a carboxylic acid through oxidation; Tollens reagent (Ag2O + NH4OH) only oxidizes RCHO.

R-X + 2 Li

Yields R-Li + LiX

R-X + Mg/(CH3CH2)_2O

Yields R-Mg-X

R-X + 2 Li followed by 2 R-Li + CuI

Yields R_2CuLi + LiI in organocuprate reagent formation (Gilman Reagent).

R-C≡C-H + NaNH_2 or R-C≡C-H + R-Li

Yields R-C≡C Na+ + NH_3 or R-C≡C-Li + RH in lithium and sodium acetylide formation.

R-M + HOR (RM = RLi, RMgX, R_2CuLi)

Yields R-H + MOR; acid-base reaction occurs with H2O, ROH, RNH2, R2NH, RSH, RCOOH, RCONH2, and RCONHR.

Ketone + [1] R"MgX or R"Li; [2] H_2O

Yields a 1°, 2°, or 3° alcohol

Ester + [1] R"Li or R"MgX (2 equiv); [2] H_2O

Yields a 3° alcohol

Acid Chloride + [1] R"Li or R"MgX (2 equiv); [2] H2O or Acid Chloride + [1] R'2CuLi; [2] H2O

Yields a 3° Alcohol or Ketone

R-MgX + [1] CO2; [2] H3O^+

Yields a carboxylic acid through carboxylation.

Epoxide + [1] RLi, RMgX, or R2CuLi; [2] H2O

Yields an alcohol with regioselectivity based on reaction conditions.

α,β-Unsaturated Carbonyl + [1] R'Li or R'MgX; [2] H2O or α,β-Unsaturated Carbonyl + [1] R'2CuLi; [2] H2O

Yields an allylic alcohol (1,2 addition) or a ketone (1,4 addition) depending on the organometallic reagent.

Alcohol + [Cl-TBS]/N (two benzene rings with two N each)

Yields a silyl ether used for alcohol protection.

Silyl Ether + Bu_4N^+ F^-

Yields an alcohol, deprotecting the alcohol.

Benzene + X2/FeX3

Yields an aryl halide (X= Cl or Br). Polyhalogenation occurs with activating substituents.

Benzene + HNO3/H2SO_4

Yields a nitro compound through nitration.

Benzene + SO3/H2SO_4

Yields benzenesulfonic acid through sulfonation.

Benzene + RCl/AlCl_3

Yields an alkyl benzene (Arene). Rearrangements and polyalkylation can occur without deactivating groups.

Benzene + RCOCl/AlCl_3

Yields a ketone without deactivating groups present.

Ester + [1] LiAlH4; [2] H2O or Ester + [1] DIBAL-H; [2] H_2O

Yields a 1° alcohol with LiAlH_4 or an aldehyde with DIBAL-H through reduction.

Carboxylic Acid + [1] LiAlH4; [2] H2O

Yields a 1° alcohol

Amide + [1] LiAlH4; [2] H2O

Yields an amine

Aryl Halide + :Nu

Yields a product if strong electron-withdrawing groups are at ortho/para positions, increasing halogen electronegativity increases rate in Add-Elim ArSN.

Aryl Halide + :Nu (harsh conditions)

Yields a product via benzyne intermediate using elimination-addition ArSN.

Alkyl Benzene + Br_2/hv or Δ or NBS/hv or ROOR

Yields a benzylic bromide

Alkyl Benzene + KMnO_4

Yields benzoic acid if a benzylic C-H bond is available.

Ketone (attached to benzene ring) + Zn(Hg), HCl or NH2NH2, OH-

Yields an alkyl benzene through Clemmenson or Wolff-Kishner reduction.

Nitro Group (attached to benzene ring) + H_2, Pd-C or Fe, HCl or Sn, HCl

Yields an aniline through reduction.

Aldehyde/Ketone + NaBH4, CH3OH or [1] LiAlH4; [2] H2O

Yields a 1° or 2° alcohol, H- adds from both sides.

Ketone + [1] R"MgX or R"Li; [2] H_2O

Yields an alcohol, R- adds from both sides.

Ketone + NaCN/HCl

Yields a cyanohydrin, CN adds from both sides.

Ketone + Ph_3P=CRR' (Wittig Reagent)

Yields an alkene + Ph_3P=O

Ketone + RNH_2/mild acid

Yields an imine, fastest at pH 4-5, intermediate carbinolamine loses H_2O.

Ketone + R_2NH/mild acid

Yields an enamine, fastest at pH 4-5, intermediate carbinolamine loses H_2O.

Ketone + H_2O with H^+ or OH- catalyst

Yields a hydrate, reversible, equilibrium favors less stable carbonyls.

Ketone + R"OH/H^+

Yields an acetal, reversible, catalyzed with acid, removal of H_2O drives equilibrium.

R-X + Ph3P then Ph3P^+-R X^- + Bu-Li

Yields Ph3P=CR, best with CH3X and RCH_2X, strong base needed for proton removal.

Cyanohydrin + OH^- + H_2O

Yields a Ketone + -CN. Reverse of cyanohydrin formation.

Nitrile + H_2O with H^+ or OH- catalyst + heat

Yields a carboxylic acid through hydrolysis.

Imine/Enamine + H_2O, H^+

Yields Aldehyde/Ketone + RNH2/R2NH through hydrolysis.

Acetal + H_2O, H^+

Yields Aldehyde/Ketone + 2 ROH through hydrolysis.

R-X + -CN

Yields R-CN + X- via SN2, where R = CH_3, 1°

R-CN + H2O/H^+ or R-CN + H2O/Base

Yields a carboxylic acid with acid and O=C-O- with base

R-CN + [1] LiAlH4; [2] H2O or R-CN + [1] DIBAL-H; [2] H_2O

Yields R-CH2-NH2 or R-CHO through reduction with LiAlH_4 or DIBAL-H respectively.

R-CN + [1] R'MgX or R'Li; [2] H_2O

Yields a Ketone

R-COOH + SOCl_2

Yields RCOCl + SO_2 + HCl

RCOCl + R'COO^-

Yields an Anhydride + $$Cl^-

Dicarboxylic Acid + Heat

Yields a Cyclic Anhydride + $$H_2O

RCOCl + H_2O

Yields RCOOH + HCl

Anhydride + H_2O

Yields 2 Carboxylic Acids

Ester + H2O/H^+ or Ester + H2O/Base

Yields Carboxylic Acid + R'OH or O=C-O- respectively.