| Question | Answer |
| Ketone: Structure | C-C-C
ll
O |
| Ester: Structure | O
ll l
-C-O-C-
l |
| Ether: Structure | l l
-C-O-C-
l l |
| Aldehyde: Structure | O
ll
C-H |
| Carboxylic Acid | O
ll
C-OH |
| Primary Amine: Structure | l
-C-NH2
l |
| Nitrile: Structure | C=-N (triple bond) |
| Primary Amide: Structure | O
ll
C-NH2 |
| Thiol:Structure | l
-C-SH
l |
| Thioether:Structure
(Sulfide) | l l
-C-S-C-
l l |
| Phenyl:Structure | C=C
/ \
C C
\\ //
C-C |
| Alkyl Halide:Structure | l
-C-X
l |
| Epoxide:Structure | O
l l
C-C |
| Peroxide:Structure | X-O
\
O-X |
| Sulfoxide:Structure | O
ll
S
/ \ |
| Boronic Acid:Structure | HO OH
\ /
B
l |
| Tert-Butanol | OH
l
CH3-C-CH3
l
CH3 |
| Isopropanol | CH3
/
OH -CH
\
CH3 |
| n-Propyl | C-C-C-n |
| Neopentyl | CH3
l
CH3-C-CH2-n
l
CH3 |
| Sec-butyl | CH3CH2CH-n
l
CH3 |
| Tert-butyl | CH3
l
H3C-C-n
l
CH3 |
| Isopropyl | CH3
\
CH-n
/
CH3 |
| n-butyl | C-C-C-C-n |
| Benzoic Acid | CO2H
l
C = C
/ \
C C
\\ //
C-C |
| Phenol | OH
l
C=C
/ \
C C
\\ //
C-C |
| Toluene | CH3
l
C=C
/ \
C C
\\ //
C-C |
| Aniline | NH2
l
C=C
/ \
C C
\\ //
C-C |
| Nitrobenzene | NO2
l
C=C
/ \
C C
\\ //
C-C |
| Benzoic Acid | CO2H
l
C=C
/ \
C C
\\ //
C-C |
| Succinic Acid | O O
ll ll
HO-C-CH2CH2-C-OH |
| Carbonic Acid | O
ll
HO-C-OH |
| Acetic Acid | O
ll
CH3-C-OH |
| Formic Acid | O
ll
H-C-OH |
| SN1 Reaction | -Monomolecular Nucleophilic Substitution.
-Involves Carbocation Intermediate (rate determining step)
-Racemization of configuration when a chiral molecule is involved |
| E1: Rate determined By: | Concentration of only ONE compound |
| SN2 Reaction: | Bimolecular nucleophilic substitution
2nd Order
-Rate determined by concentration of TWO compounds
Nu(-) + R-L --> {Nu---R---L} --> Nu-R + L(-)
Backside replacement |
| Hemicetal Production Mechanism | Hydrogen Attacks O (partial neg)
-->creates carbocation
-H from alcohol quickly attacks carbocation, expels proton
---> recreates catalyst |
| Carbanion | C(-) |
| Carbocation | C(+) |
| Oxidation | Increasing Oxygen content OR decreasing Hydrogen content |
| Alpha Particle | Doubly positively charged helium nucleus |
| Steric Factors | Large or bulky groups near a reaction site that hinder the reaction's progression |
| Substitution Reaction | One atom or group is substituted (replaced by another) |
| Salts | Ionic compounds that conduct electricity and are crystalline solids at room temperature |
| Amphoteric | A substance that can act as both an acid and a base |
| pH | Measure of acidity
-log [H(+)] |
| Lewis Acid | Substance accepting electrons |
| Lewis base | Substance donating electrons |
| Bronsted-Lowry Base | Substance that accepts a proton |
| Bronsted-Lowry Acid | Substance donating a proton |
| Secondary alcohol + CrO3/K2Cr2O7/KMnO4 | Ketone |
| Primary alcohol + KMnO4 --(under abrasive conditions)-->
{acidic/in presence of -OH} | Carboxylic Acids |
| Mild Oxidizing Agents | CrO3
K2Cr2O7
or
KMnO4 @ room temperature + neutral pH |
| Major Product | Most stable of the possible products of a reaction |
| Minor product | Less stable of the possible products of a reaction |
| Alcohols | An alcohol is any organic compound in which a hydroxyl group (-OH)
is bound to an alkyl or substituted Alkyl group
IR abs: 3200-3650 (KNOW THIS) |
| Ortho | (of rings)
1,2 |
| Meta | (of rings)
1,3 |
| Para | (of rings)
1,4 |
| Angstrom | 10 ^ -10 Meters |
| Aromatic Compounds | Cyclic compounds which have their pi electrons delocalized across the whole ring |
| Alkene (definition) | An unsaturated chemical compound containing at least one carbon-to-carbon double bond |
| Axial Substituents | These substituents (generally) perpendicular to the ring |
| Equatorial Substituents | Those in the same plane as the carbon ring |
| Nucleophile | Molecule with a free pair of electrons and sometimes have a negative charge
ex: OH(-), CN (-) |
| Electrophiles | Substances which seek electrons |
| Achiral | Optically Inactive |
| Configuration | Absolute three dimensional arrangement |
| Specific Rotation | An inherent physical property of a molecule, measuring the rotation of plane polarized light by a substance.
Observed rotation (degrees)
Alpha= ---------------------------------
(Tube Length (dm)) x (Concentration (g/ml) |
| Dextrorotary | A substance that rotates plane polarized light in a clockwise direction |
| Levrorotary | A substance that rotates plane polarized light in a counterclockwise direction |
| Meso Compound | Achiral (optically inactive) disastereomer of chiral stereoisomers |
| Plane Polarized Light | Light that oscillates in only one plane |
| Carbonyl Group | C=O |
| Markovnikoffs Rule | The nucleophile will be bonded to the most substituated carbon.
The Electrophile will be bonded to the least substituted carbon |
| Benefits of H2O | High Heat Capacity, High heat of vaporization, polar solvent properties, Reactivity, Cushions organs |
| Radical Propagation | Free radical begins a series of reactions creating new free radicals.
CH4 + Cl * --> *CH3 + HCl
*CH3 + Cl2 --> CH3Cl + Cl* |
| Acetal | Composite functional group in which two ether functions are joined to a C bearing a H and an alkyl group |
| Ketal | Composite functional group in which two ether functions are joined to a carbon bearing two alkyl groups |
| Hemiacetyl/ Hemiketal | OH
l
R-C-R'
l
OR''
R' determines ketal/acetal |
| Aldol Condensation | A base catalyzed reaction of aldehydes and ketones that have alpha hydrogens.
Intermediate Aldol: Alcohol + Aldehyde
Aldol undergoes a dehydration reaction producing C-C bond in condensation product, and enal |
| Enal | Aldehyde + Alkene |
| Aldol | Substance which is both aldehyde + alcohol |
| Gringard Reagent | RMgX |
| Alkyl Lithium | RLi |
| Carboxylic Group | R-C=O
l
OH |
| Dimerization | Hydrogen bonding between like substances |
| Oxidizing tertiary alcohols | -Difficult process
Under acidic conditions, a tertiary alcohol can be dehydrated, hen oxidized |
| Good "leaving groups" have | Strong conjugate acids |
| 'E' designation | Substituents on a double bond and given priority.
If two highest priority groups are on opposite sides, it is assigned E configuration
E=entegegen=Opposite |
| Radical Substitution Reactions (steps) | -initiation
-propagation
-termination |
| Ozonolysis | Oxidation of alkenes
O3 reacts vigorously with alkenes
-Leads to an oxidative cleavage of double bond, creating a ketone and an aldehyde |
| Acidity of alpha hydrogen | Alpha hydrogen is attatched to the carbon next to the carbonyl group. It's acidity increases if in between carbonyl groups |
| Naming of ketones/aldehydes | Replace "e" of corresponding alkane with:
-'al' for aldehydes
-'one' for ketones |
| Naming an alcohol | Replace the 'e' of corresponding alkane with '-ol' |
| SN1 Reaction Rates for Carbon (groups) | Benzyl=Allyl >tertiary > alcohols > secondary alcohols > primary alcohols |
| Enantiomers | Two non-superimposable diastereomers which are mirror images of one another.
-must be chiral |
| A substituent is a "good leaving group" if | It has a strong conjugate acid |
| Benzene's C-C bond | Only known to have one type, with a bond length of 1.4 A |
| Electron Shell Repulsion | All atoms (thus, molecules) are surrounded by an electron shell, or electron cloud. Since like charges repel, the negative charges repel one another |
| Isomer | Different molecules with the same number and type of atoms |
| Conformational Isomers | Isomers which differ only by the rotation about multiple single bonds (or just one single bond) |
| Structural Isomer | (aka constitutional isomers)
Isomers in which atoms and/or bonds differ in relation to one another |
| Stereoisomers | Different compounds with the same structure differing only in spacial orientation of atoms |
| Geometric Isomers | Isomers that occur in rings and alkenes due to their inability to rotate. Results in Cis/Trans compounds |
| Diastereomer | Any pair of stereoisomers that are NOT enantiomers.
-Both chemically and physically different from one another |
| E2 Reactions | Require strong bases like KOH or the salt of an alcohol. (sodium alkoxide)
Rate determined by concentration of TWO reactants |
| Important features of SN1 reactions in alcohols | First Order
Racemization if chiral molecule
Stable carbonium should be involved |
| Electrophilic Aromatic Substitution | Similar to SN1 mechanism
-Occurs with electrophilic reagents and leads to a rearrangement which produces a substitution
-Intermediate positive charge stabilized by resonance |
| Bromination | Br/FeBr3 is used to generate the Br+ species which is highly electronegative (can react w/ aromatic rings) |
| C=C
/ \
C C + E(+) ------>
\\ //
C-C | 3 Products differing in relative positions of E and C(+)
E Cannot be on carbocation, only three locations for C(+) relative to double bond are possible. |
| Dehydration of Alcohols (Mechanism) | Proton (H+) is attracted to negative charge of -OH, forming a water which is a good leaving group.
---> electrons are attracted to the positively charged carbon causing a proton to leave, forming an alkene |
| Alcohol substitution reaction | The -OH group is replaced (substituted) by a halide (usually Cl or Br)
2 Types: SN1/SN2
Reagents: HCl, HBr, PCl3 |
| Elimination Reactions | Occur when an atom or group of atoms is removed(eliminated) from adjacent carbons, leaving a multiple bond.
C-C ---> C=C |
| Alkene electrophilic addition | Electrophile is added to alkene via a carbocation intermediate |
| Alkene Oxidation | Alkene + KMnO4 (under acidic conditions) creates a dialcohol (glycol)
Under extreme heat, an oxidative cleavage of double bond occurs |
| Alkene Hydrogenation | Alkenes react with hydrogen in the presence of a variety of metal catalysts (ex: Ni, Pd, Pt) |
| Electrophile in aromatic substitution | Must be a powerful electrophile
-b/c resonance stabilized ring is resistant to most types of routine chemical reactions |
| SN1 reaction in alcohols | Transition state involves a carbocation, whose formation is the rate determining step
-benzyl, allyl, primary, secondary alcohols
- all use this mechanism |
| SN2 Reaction | -Mechanism by which primary alcohols are substituted
-2nd Order
-Nucleophile adds to backside
-inverts configuration if optically active
-Steric factors affect reaction rate |
| E2 Reaction Mechanism | 1. Base eliminates proton, giving carbon a negative charge
2. Electron pair quickly attracted to other carbon's partial positive charge (b/c of Br electronegativity) forming a double bond while Br is bumped simultaneously b/c carbon can only have 4 bonds |
| E1 Reaction | Rate of reaction depends upon the concentration of one compound.
Can occur as a minor reaction alongside SN2 reaction or as a major produc in alkyl halides or some alcohols |
| Meta Directors: Mechanism | Partial positive charges are located at the ortho and para positions with no substituents, forcing the electrophile to the meta position in avoidance of positive charge |
| Carbocation/Carbanion + Bond location relative to substituent | Carbanion l Dbl Bond locations
2 l 3,5
4 l 2,5
6 l 2,4 |
| Meta directors | -Deactivating groups which slow reaction relative to unsubstituated Benzene
-Withdraws electrons from ring, making it less attractive to electrophiles
-Works through carbanion |
| O/P Directors | Activating group donates electrons to ring, giving the group a pos charge, and one carbon on the ring a neg charge. Neg charge is passed along the ring until group's initial double bond is broken.
-Causes a reaction rate increase rel. to benzene |
| Important factors of carboxylic acid chemistry | H is weakly acidic b/c of partially neg O, and resonance
Carboxyl carbon was susceptible to Nu(-) attack
Good(in acid, great) leaving group
H bonding is possible inner or intra molecularly |
| Low molecular weight acids: characteristics | Liquids with strong odors and high boiling points.
-due to polarity + H bonding of molecule
H Bonding = water soluble |
| R,S System | R configuration: Clockwise rotation after prioritization
S Configuration: Counterclockwise order of priority |
| Combustion Equation | C(n)H(2n+2) + Excess O2
----->
nCO2 + (n+1)H2O |
| Ring Strain | Results from the bending of the bond angles in greater amounts than normal |
| Carbocation Stability | Tertiary>Secondary>Primary |
| Cyclohexane Stability | Chair Conformation > Boat Conformation
-99% in chair conformation |
| ------------>
OH(-)/H2SO4/H2O | Oxidizer
Adds double Bond |
| ------------>
2NaNH2/H3O(+) | Forms third bond
Turna alkene to alkyne |
| H2O/H2SO4
------------>
HgSO4 | Hydration
Adds -OH and H(+) groups |
| KOH
------------->
Ethanol | Oxidizer
Creates 2nd/3rd bond |
| 1.Hg(OAc)2, H2O/THF
------------------>
2. NaBH4 | Dehydration
Adds alcohol Group |
| Meta Position Deactivators: | -CHO
O
ll
COH
O
ll
COCH3 |
| O/P Activators | -CH3
-NH3
-OH |
| Ortho/Para Deactivators | -Br
-F
-Cl
-I |
| Aromatic Rules: | 4n+2 pi electrons
-conjugated ring |
| -RCONR2 | Carboxamide |
| SN2 reactivity by carbon placement | Tertiary>Secondary>Benzene>Primary>Methyl
-Due to increasing ability of incoming group to access carbon
-Decreasing steric interaction |
| Leaving group reactivity | OH>NH2>F>Cl>Br>I>TosO(-)
-based on electronegativity |
| O3 OR KMnO4
------------> | Oxidative cleavers
Break completely between two carbons
Internal C=C : Terminal C=C:
C=O + C=O O=C=O + O=C=O
l l
OH OH |
| |
