E1: SOLUBILITY OF ORGANIC COMPOUNDS

Solubility Class Description Example

- Extent to which a solute mixes homogenously with a Soluble – water
S1
solvent Soluble – ether
Dissolution Soluble – water
S2
Inoluble – ether
- A process of going into solution Strongly acidic
- Affected by: A1
Soluble – NaOH, NaHCO3
1. Similar IMFA Weakly acidic
a. H-bonding A2 Soluble – NaOH
b. Dipole-dipole Insoluble – NaHCO3
c. Dipole-induced dipole
d. Ion-induced dipole B Basic
e. Induced dipole-induced dipole
(London dispersion forces) M Miscellaneous neutral
f. Ion-ion Inert
2. Chemical reaction Insoluble – everything but
a. Neutralization I water

m
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Polarity Saturated compounds,
hydrocarbons, aromatics

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- Description of the distribution of charges within a Neutral/very weak base

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molecule N H2SO4 forced protonation

o.
Oxygen-containing

Organic rs e
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compound Class S
- Water-soluble compounds
o Limited: 5 carbons or less per H-bonding
insoluble+
o

soluble + group
diethyl ether
aC s

5% NaOH - H-bonding groups:

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o ROH alcohol
o RC=OOH carboxylic acid
S2 S1 insoluble + soluble + o RNH2 amine
5% HCl 5% NaHCO3 o RC=ONH2 amide
o RC=O carbonyl
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o ROR ester
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B A2 A1
insoluble S1 S2
Polar Highly polar
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Ether soluble Insoluble

with N or S + conc. H2SO4
Th

Slightly H2O soluble

M I N Class A
- NaOH-soluble compounds
- Acidic groups:
o R=COOH carboxylic acids
o Ar-OH phenols (rel. weaker)
A1 A2
Strongly acidic Weakly acidic
NaHCO3 soluble Insoluble

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 Class B o Single solvent + water
o Mixed solvent + water + ethanol
- HCl-soluble
2. Heat
- Basic groups
3. Charcoal (very small amount)
o RNH2 amine
o Adsorption of colored impurities
Class M 4. Hot filtration
o Avoid premature recrystallization
- Have N – not basic
(↓ %recovery)
- Have S – not acidic
 Fluted filter paper
- Groups
 Short-stemmed funnel
o RC=ONH2 amide
 Pre-heated receiving flask (or w/
o R-NO2 nitro
hot water)
Class N 5. Cool to room temperature
o Slow cooling – allow particle growth
- Conc. H2SO4-soluble
o Large crystals
- Neutral/very weak bases (benzaldehyde, benzyl
 High filterability
alcohol)
 ↑ %purity – less SA exposed
- Forced protonation  salt + water
6. Filter + wash crystals
- N/S/O-containing compounds
o Cold solvent – prevent redissolution
- Unsaturated compounds (electron-rich)

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- ROH + H2SO4 ⇄ ROH2 + HSO4-

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PARAMETER RECRYSTALLIZATION SUBLIMATION
RC=O + H2SO4 ⇄ RC=OH+R + HSO4-

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-
- RC≡N + H2SO4 ⇄ RC≡NH+ + HSO4- Procedure Tedious Simple and easy

o.
Class I Many steps Single step,
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- Insoluble in all no solvent
- Saturated compounds, aromatics, alkyl halides
% yield High Low
% purity Low High
o

E2: RECRYSTALLIZATION AND MELTING POINT

aC s

DETERMINATION OF BENZOIC ACID

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Solvent E3: EXTRACTION AND PURIFICATION OF CAFFEINE

- Solute should be: Solvent extraction (liquid-liquid)

o Soluble at high temp - Based on affinities in two immiscible solvents
o Slightly soluble at room temp
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- Impurities – insoluble Sublimation technique

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- Selective recrystallization - Sublimation: solid  gas

- No reaction with the solvent - Deposition: gas  solid
- Sufficient volatility - Requires:
- BPsolvent < MPsolute - solute stays solid
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o ↑ vapor pressure < melting point

- Non-toxic - Caffeine:
Th

- Non-flammable o Melting point: 238°C

Failure to recrystallize o Sublimation point: 178°C

- Supersaturated solution Limitations:

o Seeding – add a small amt of pure solute - Not all solids satisfy the requirement
o Scratch inner walls - Time constraint - ↓ %recovery
- Unsaturated
o Boil off excess solvent Procedure

Assessment of purity 1. Sample + hot water

o ↑ solubility of caffeine
- Narrow MP range o Extraction of other compounds
- Close to theoretical MP 2. + Ethyl acetate
o Impurities – ↓ MP o Saponins – amphiphilic (polar and nonpolar)
Procedure 3. + NaOH, + dH2O
o Tannins (polyphenols) – acidic
1. Crude benzoic acid
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 4. + CaCl2 E5: ISOMERISM AND STEREOCHEMISTRY
o Remove residual H2O
5. Evaporate solvent Isomers
o Crude caffeine
o Pure: white, crystalline, odorless Constitutional/Structural Stereoisomers
Isomers

E4: PAPER CHROMATOGRAPHY Conformational

Paper chromatography
Geometric
- Separate mixtures
NORMAL REVERSE
Optical
Stationary phase Polar Nonpolar
Mobile phase Nonpolar Polar - Constitutional
o Same formula, different arrangement
- Stereoisomers
Liquid-liquid; Normal o Same formula, same arrangement, different
orientations in space

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- SP: water adsorbed on cellulose

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o Conformational
- MP: solvent (via capillary action)  Free rotation about a single bond

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giving rise to different isomers

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Solvent
 Torsional strain
- Moderately volatile  Eclipsing

o.
- Good resolving power – no tailing
- Non-toxic rs e  Steric strain
 Bulky groups
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- Cheap o Geometric (cis-trans) isomers
Chromatographic chamber  Restricted rotation about a double
bond or a ring structure
o

- Closed system – avoid volatilization  ↓ [MP]  Cis-trans

- Saturate chamber with MP vapor
aC s

 Same group
- Paper should not touch the sides of the chamber
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 E-Z
- Unimpeded uniform rise of the MP  Different groups
- Solute sample – (prioritized)
o Not below the solvent level
 Cahn-Ingold-Prelog rules
o Just enough (too much will leave a tail, too
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o Optical
little will not show spots)
 Not superimposable
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- Slow rise of MP
 Can rotate plane-polarized light
o Open chamber
 Optically active  chiral
o Thick paper
 Enantiomers
Spot detection  Mirror images
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 Not superimposable
- Under visible light
Th

 Diastereomers
- Iodine chamber  detect unsaturated compounds
 Non-mirror images
Retention factor  Not superimposable
- Good resolution: Rf = 0.4 – 0.8  Meso copounds
 Superimposable
𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑟𝑎𝑣𝑒𝑙𝑒𝑑 𝑏𝑦 𝑠𝑜𝑙𝑢𝑡𝑒  Identical
𝑅𝑓 =
𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑟𝑎𝑣𝑒𝑙𝑒𝑑 𝑏𝑦 𝑠𝑜𝑙𝑣𝑒𝑛𝑡  Optically inactive

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 E6: PREPARATION AND PURIFICATION OF AN ALKYL HALIDE  More accurate
o Continuous flow of water
- Nucleophilic substitution reaction
 Condensation is maximized
SN1 SN2 o Sealed joints
 Prevent volatilization
Unimolecular Bimolecular
Two steps One step
E7: ALCOHOLS, PHENOLS, AND ETHERS
3° > 2° > 1° > CH3 CH3 > 1° > 2° > 3°
Lucas Baeyer’s
R  R+S RS
Ethanol None after 10m Brown ppt,
Non-stereospecific Stereospecific decolorization
Rate = k[RX] Rate = k[RX][Nu-] Isopropyl alcohol 5m Brown ppt,
decolorization

GOOD T-BuOH Immediately Purple solution

Electrophile (E+) Nucleophile (N-) Leaving groups Benzyl alcohol Immediately Brown ppt,
decolorization
Electronegative Large/↑ # of e- Stable

m
Diethyl ether Purple solution

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EWG ↑ polarizability Weak base

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(NH3/H2O

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Halides Lucas Test

o.
t-BuOH HCl OH (strong base) - Differentiate 1°, 2°, 3° alcohols

rs e o + Layer formation: 3° > 2° > 1° > CH3

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- ZnCl2, conc. HCl
HX reactivity - Favors SN1 reaction
o Acidic medium  protonate OH-  H2O
- HF < HCl < HBr <HI (better leaving group)
o

o Zn2+ - Lewis acid – electron pair acceptor

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o Highly ionic/polar medium  promote

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SN1 t-BuOH + H+  t-BuOH2 + Cl-  t-BuCl + H2O carbocation formation

E1 2-methyl propene - Relies on solubility difference of alcohols and alkyl
halides
- Only 5 Carbons or less  soluble with Lucas rgt.
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Procedure Baeyer’s Test

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1. Cold concentrated HCl - Differentiate 1° and 2° from 3° alcohols

o Prevent volatilization - KMnO4 (strong oxidizing agent)
o Minimize side reactions - At least one alpha hydrogen
 2-methylpropene
sh is

- + brown precipitate (MnO2); decolorization

 Di-tert-butyl ether - Primary  carboxylic acids
2. Separatory funnel + NaCl
Th

- Secondary  ketones
o Salt-out agent - ↑ polarity of aqueous layer, - Ethers –
more distinct layers o do not decolorize
3. Organic layer + solid NaHCO3 o Inert to oxidation by MnO4-
o Neutralize excess HCl - Phenol  Ketone
o Aqueous NaHCO3 – introduce water
o Effervescence – indicator of the pH FeCl3 Br2 in H2O KMnO4
neutralization reaction
Phenol 5 Violet White Brown ppt
4. Filtrate + CaCl2
o Remove water formed and excess alcohol p-nitro 3 Red
o Prevent hydrolysis
Picric 1
5. Simple distillation
o Boiling chips Β-naphthol Green
 Distribute heat evenly
p-bromo Yellow
 Prevent superheating
o Vapor temperature measured (not liquid’s)
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 Acidity of phenols Hexane Limonene Benzene
- Electron withdrawing groups  more acidic State Liquid Liquid liquid
Bromination of phenols Color Colorless Yellow Colorless
- Br2 in H2O (Lewis acid) H2O Insoluble Insoluble Insoluble
- E+AS
Density Less dense Less dense Less dense
FeCl3
T-BuCl/AlCl3 Yellow Yellow Orange
- Complexation [R3Fe] (FC’s crystals crystals crystals
alkylation)
Br2, light Colorless Colorless Smoky
E8: ALIPHATIC AND AROMATIC HYDROCARBONS
(FRS) yellow
Alkanes
Br2, dark Red orange Colorless Red orange
- Inert
KMnO4 Purple Brown ppt, Purple
- Free radical reactions – require light/heat
solution decolorization solution
Alkenes/alkynes
Combustion Blue, Yellow, Yellow,

m
- Loosely held pi electrons  reactive

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non-smoky non-smoky smoky
- Reactivity: alkenes > alkynes

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- Electrophilic addition reactions

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Aromatics E9: RELATIVE RATES OF ELECTROPHILIC AROMATIC

o.
- Special stability due to resonance SUBSTITUTION
-
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Electrophilic aromatic substitution ELECTRON DONATING (o,p)
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- Huckel’s rule
o # of pi electrons = 4n + 2 Strong -OH
-NH
Distillation -NHR
o

- Simple – 30°-50°C difference -NR2

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- Fractional – 5°-10°C difference Moderate -OR

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- Steam – decompose before boiling point NHCOR

- Reduced pressure Weak -C6H5
Alkyl groups
Steam distillation ELECTRON WITHDRAWING (o,p)
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- Immiscible phases (steam, limonene) Halogens -F

o Ptotal = P°steam + P°limonene -Cl
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- Boils when Ptotal > Patmospheric -Br

- Requires a lower temperature at which the sample -I
boils ELECTRON WITHDRAWING (m)
Moderate -CN
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- For heat sensitive compounds

-COOH
Tests
Th

-COOR
- Br2, light/dark + brown to colorless -CHO
o Light – alkanes (FRS) -COR
o Dark – alkenes, alkynes (E+A) -CONH2
- Alkylation + orange crystals -SO3H
o Aromatic compounds Strong -NO2
- Baeyer’s/KMnO4 + decolorization, red ppt -NR3+
o Unsaturated compounds, phenols, 1°/2° OH -CX3
- Combustion
o Higher C:H ratio and heat resistance – C
released as soot

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