ACS Organic Chemistry I & II Reactions Reagents, and Functional Groups

Alcohol

Ketone

Amine

Ether

Amide

Ester

functional groups

Alkyl

An alkane missing a hydrogen

Aromatic compound

Cyclic, planar, with every atom of the aromatic ring having a p orbital, while obeying hackles rule of 4n+2 pi electrons

Vinyl

Hydrolysis Reaction

Carboxylic Acid

pKa ~ 5

Enantiomers

stereoisomers that are non super imposable mirror images

Diastereomers

- Same molecular formula, same bond connections, NOT mirrors images, NOT the same compound.

Stereocenter

sp3 hybridized and bounded to different subsitutents

Chiral

objects with non-superimposable mirror images; 'handedness'

Meso

Achiral compound that contains stereocenters

Cahn-Ingold Prelog

R/S Nomenclature

E2

3⁰ with strong base, 2⁰ with strong base, 1⁰with strong, non-nucleophilic base

E1

3⁰ with weak base in polar, protic solvents, 3⁰ in polar, protic solvents, with poor nucleophiles, 2⁰ with poor nucleophiles in polar, protic solvents

SN2

1⁰ with strong bases, 1⁰with weak bases, 2⁰ with weak bases

SN1

2⁰ or 3⁰ in weak bases or poor nucleophiles in polar, protic solvents

CH₃OK/CH₃OH

Favors SN2 or E2

Acetone

SN2

OH⁻

Nucleophilic Displacement Reaction

Nucleophile

Electrophilic Additions

Attracted to C=C because of it being oxygen rich

Forms a carbocation intermediate that rearranges to a more stable carbocation that is immediately susceptible to nucleophilic attack, completing the addition to the double bond. Attack is on most stable carbon.

CH₃OH/H⁺

The H⁺ attacks first. The oxygen of the methanol is the nucleophile

NaH

ROH to RO- Na+

NaBH4, MeOH

Ketone to alcohol

H2/Pt

Reducing to cis

1. LAH 2. H2O

Reducing to trans

1. RMgX 2. H2O

Add R group

TMSCl, Et3N

Protection group of alcohols

TBAF

Remove alcohol protecting group

1. TsCl, py 2. NaBr

Make water good leaving group. The sn2

SOCl2, py

Chlorination of alcohol

H2SO4, heat

Elimination

-OEt

Elimination

Jones

Secondary alcohol= ketone

Primary alcohol= carboxylic acid

PCC

Primary alcohol= aldehyde

1. Hg(OAc)2, H2O or ROH 2. NaBH4

Markinov addition

MCPBA

Epoxide ring

1. Br2, H2O 2. NaOH

Epoxide ring

NaOH, H2O

Opening epoxide ring

1. Nuc 2. H2O

Opening epoxide ring

HX

Markinov addition

HBr, ROOR

Anti markinov

1. BH3.THF 2. H2O2, NaOH

Anti markinov n syn

OsO4

Syn OH addition

Electro cyclic

Syn hv syn

Syn heat anti

Anti heat syn

Anti hv anti

NBS heat

Free radical bromination

Na, CH3OH, NH3 Birch reduction

Aromatic ring to two alkynes

FeBr3, Br2

Bromination of aromatic ring

AlCl3, Cl2

Chlorination of aromatic ring

Fuming H2SO4

Sulfonation of aromatic ring

Dilute H2SO4

Remove sulfonation of aromatic ring

HNO3, H2SO4

Nitration of aromatic ring

1. KMnO4, NaOH heat 2. H3O+

Methylbenzene to methyl carbolic acid

HO--OH

Acetal protecting group

H2O

Remove acetal protecting group

Witting reaction

C=C produced

RCO3H

Produced esters

1. CO2 2. H3O+

Grignard to carboxylic acid

1. LDA 2. RX

Alkylation to alpha

Low temp less sub

High temp more sub

Sulfuric acid

Proton source

NaNH2

Elimination

PBR

Bromination of primary alcohol

Heat

Cyclo reactions

1. DIBAH 2. H2O

Ester into aldehyde

SN1

-2 steps

-Rate limiting step, so reaction rate is dependent on concentration of R-X

-Weak nuc/weak base (typically solvolysis) for secondary and tertiary carbons; also competes with E1 reactions

SN2

-1 step (concerted)

-Reaction rate is dependent on concentration of R-X and Nuc

-Prefers methyl, primary, or secondary carbons

-Strong nuc/strong base (OH-) or strong nuc/weak base (I-, CH3CO2-) required for methyl, primary, and secondary

E1

-2 steps

-Rate limiting step, so reaction rate is dependent on concentration of R-X

-Weak nuc/weak base (typically solvolysis) for secondary and tertiary carbons; competes with SN1 (without heat)

E2

-1 step

-Reaction rate is dependent on concentration of R-X and Nuc

-Weak nuc/strong base (potassium tert butoxide or LDA) for primary carbon

-Strong nuc/strong base or weak nuc/strong base for secondary and tertiary carbon

-Beta hydrogen must be anti to leaving halide

Hydrohalogenation of alkenes

-Reagents: HCl, HBr, or KI + H3PO4

-Addition

-Carbocation intermediates, rearrangements possible

-Markovnikov addition

-No stereochemical preference

Radical hydrohalogenation of alkenes

-Reagents: Peroxides, heat/light

-Chain reaction

-Radical intermediates

-Anti-Markovnikov addition

-No stereochemical preference

Halogenation of alkenes (anti addition)

-Reagents: Br2, Cl2, or I2 in CH2CL2 or CCl4

-Addition

-Bromonium or chloronium intermediates

-Anti addition stereochemical preference

Halohydrin

-Addition of X2

-Reagents: Br2 or Cl2 in H2O

-Bromonium or chloronium ion intercepted by H2O

-Markovnikov addition of H2O

-Anti addition stereochemical preference

Acid-catalyzed hydration of alkenes

-Reagents: H2SO4, HClO4, H3PO4; high temperature

-Can be reveresed to form alkenes from alcohols

-Addition

-Carbocation intermediates

-Markovnikov addition

-No stereochemical preference

Oxymercuration-demercuration of alkenes

-Reagents: 1) Hg(OAc)2 in H2O or THF/H2O, 2) NaBH4

-Addition of mercury compound

-Mercurinium ion intermediate intercepted by H2O

-Markovnikov addition of H2O

-Addition of H2O is anti, but reduction (NaBH4) scrambles stereochemistry, no preference

Hydroboration of alkenes

-Reagents: 1) BH3-THF (Forms trialkylboranes/R3B), 2) H2O2/-OH; room temperature or heat

-Addition of BH3

-Cyclic transition state puts boron on least substituted carbon of the double bond

-Syn addition stereochemical preference

-Anti-Markovnikov addition of -OH

Hydrogenation of alkenes

-Reagents: H2 over metal catalyst (Pd/C, Pt, PtO2)

-Surface reaction

-Syn addition from the less crowded/sterically hindered face

Hydroxylation of alkenes (syn addition)

-Reagents: KMnO4/-OH (lower yield) or OsO4/pyridine (higher yield, but dangerous and expensive) or catalytic OsO4 with NaHSO3

-Cyclic transition state and intermediate

-Syn addition of -OH groups

Ozonolysis of alkenes

-Reagents: 1) Ozone (O3) at low temperature, 2) Zn/AcOH

Oxidation of diols

-Reagents: 1,2-dioltreated by HIO4 in H2O/THF

-Cyclic intermediate with HIO4

Oxidation of alkenes with permanganate

-Reagents: potassium permanganate (KMnO4) under acidic/neutral condition (H+)

-Oxygen inserts into all former vinylic C-H bonds

Hydrohalogenation of alkynes

-Reagents: HCl, HBr in acetic acid

-Addition

-Vinyl halide as intermediate

-Markovnikov addition

-Mixed stereochemistry, but first addition is usually trans, often followed by second addition (less reactive than alkenes)

-Excess HX --> geminal dihalides and excess X2 ---> tetrahalides

Halogenation of alkynes

-Reagents: Br2 or Cl2 in CCl4

-Addition

-First addition is usually trans

-Markovnikov addition

-Excess X2 ---> tetrahalides

Hydration of alkynes (HgSO4)

-Reagents: HgSO4/H2O/H2SO4

-Addition catalyzed by Hg2+, no mercurinium ion invovled

-Primary product is an enol (less stable tautomer of a ketone)

-Markovnikov addition

Hydroboration of alkynes

-Reagents: 1) BH3/THF, 2) H2O2/OH-

-Two-step addition of borane followed by oxidation with basic hydrogen peroxide (H2O2)

-Syn addition only (keto-enol tautomerization) for disubstituted alkynes

-Anti-Markovnikov addition with terminal alkynes; forms aldehydes

Hydrogenation of alkyne to alkene

-Reagents: H2 and Lindlar's catalyst (cis product) or Na, NH3 (trans product)

Alkylation of acetylide anion (Organic synthesis)

-Reagents: 1) NaNH2, 2) R1X

-Only occurs with terminal alkynes and occurs best with primary alkyl halides

Opening of epoxides/Anti dihydroxlation

Oxidative cleavage of alkynes

-Reagents: 1) O3, 2) H2O

-Terminal yields carboxlyic acid and CO2

-Disubstituted yields two carboxlic acids

Synthesis of alkynes

-Elimination of halides (E2)

-Vicinal dihalide (alkane) ---(2 eq. KOH, ethanol or 2 NaNH2, NH3)--> alkyne

-Vinylic halide (alkene) ---(NaNH2/NH3)--> alkyne

Keto-enol tautomerism

-Conversion of enols to ketones

-Occurs in hydroboration of alkynes and

hydration of alkynes with HgSO4

regioselective

preference of one direction of chemical bond making or breaking over all other directions

stereospecific

single reactant forms an unequal mixture of stereoisomers

regiospecific

one structural isomer is produced exclusively when others are theoretically possible

radicals

form when bonds break homolytically via heat, using fishhook arrows to indicate single electron movement

very unstable, but can be stabilized by resonance/hyperconjugation; radical reactivity follows radical stability trend (tertiary > secondary > primary); geometry of free radical carbon allows for halogen abstraction to occur on either side of the plane with equal probability