![Page 1: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/1.jpg)
Chapter 1 1
ORGANIC CHEMISTRYSTUDY OF CARBON-CONTAINING COMPOUNDS
CH
H
H
H
MethaneHO
Complicated organic molecule
![Page 2: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/2.jpg)
Chapter 1 2
SHORT HISTORY OF CHEMISTRY
PRE-1828 ERA
TWO MAJOR DISCIPLINES EMERGING
INORGANIC - MINERAL CHEMISTRY
ORGANIC CHEMISTRY - PLANTS AND ANIMALS
![Page 3: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/3.jpg)
Chapter 1 3
ORGANIC COMPOUNDSCHARACTERISTIC PRODUCTS OF LIVING ORGANISMS
SUBSTANCES LIKE SUGAR AND OLIVE OILINORGANIC COMPOUNDS
PRODUCTS FROM NON-LIVING ENVIRONMENT
SUBSTANCES LIKE WATER AND IRON
BERZELIUS’ DEFINITIONS
![Page 4: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/4.jpg)
Chapter 1 4
Vital Force Theory
INORGANIC MATERIALS COULD BE CONVERTEDTO ORGANIC MATERIALS IN THE PRESENCE OF A VITAL FORCE FOUND ONLY IN LIVING BODIES.
![Page 5: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/5.jpg)
Chapter 1 5
In addition to Vital Force Theory
Organics hard to purify
Appeared to violate the Law of Definite Proportions
Organic Little Studied
Isomerism problem - same molecular formula butDifferent compounds
Consider ethanol and dimethyl ether
![Page 6: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/6.jpg)
Chapter 1 6
Woehler’s urea synthesis
Ammonium isocyanate + heat ------> urea
NH4CNONH2CONH2
“I have been able to make urea without aid of kidneyof man or dog.
1828
1828
![Page 7: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/7.jpg)
Chapter 1 7
Deutsche Museum
![Page 8: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/8.jpg)
Chapter 1 8
STYLES
![Page 9: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/9.jpg)
Chapter 1 9
Schubert
![Page 10: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/10.jpg)
Chapter 1 10
Liszt - Young
![Page 11: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/11.jpg)
Chapter 1 11
BIRTHSJULES VERNE - AROUND THE WORLD IN 80 DAYS
LEO TOLSTOY - ANNA KORNINA
HANS CHRISTIAN ANDERSON
MARRIAGESBARTHOLOMEW HEIFNER AND POLLY GRISHAM.IN SHELBY COUNTY, ENGLAND
![Page 12: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/12.jpg)
Chapter 1 12
IMPORTANT EVENTSANDREW JACKSON ELECTED PRESIDENT OF USA DEFEATED JOHN Q. ADAMS
RUSSO-PERSIAN WAR ENDED
FATH ‘ALI SHAH’ AND RUSSIAN COUNTERPARTSIGNED TURKMANCHAI TREATY
GAVE RUSSIA - GEORGIA, ARMENIA, AND AZERBAIJAN
![Page 13: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/13.jpg)
Chapter 1 13
Post 1828•Over 18,000 million compounds have been synthesized
•Pharmaceuticals
•Biochemicals
•Plastics
•Agrichemicals
•Paints
![Page 14: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/14.jpg)
Chapter 1 14
Why so many organic?
H O N X P S Se
FORMS COVALENT BONDS WITH MANY METALS
Li Mg Al Cd Fe
FORMS COVALENT BONDS WITH NON-METALS
![Page 15: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/15.jpg)
Chapter 1 15
WITH ITSELF
CC
CC
C
CHAINS
CCH
CCH
C
CHAINS WITH BRANCHES
C CC
CC
C
CC
RINGS
No limit
AND
![Page 16: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/16.jpg)
Chapter 1 16
Allotropic Forms of Carbon
Graphite --layers of carbon atoms
Diamond -- 3-D tetrahedral
Buckmeisterfullerene (Bucky Ball) -- Soccer ball
![Page 17: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/17.jpg)
Chapter 1 17
Atomic Structure
• protons, neutrons, and electrons
• isotopes
C12
6 6C14
=>
![Page 18: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/18.jpg)
Chapter 1 18
Atomic Orbitals
2s orbital (spherical)
2p orbital =>
![Page 19: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/19.jpg)
Chapter 1 19
Electronic Configurations
• Aufbau principle: Place electrons in lowest energy orbital first.
• Hund’s rule: Equal energy orbitals are half-filled, then filled.
=>
![Page 20: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/20.jpg)
Chapter 1 20
Table 1-1
=>
![Page 21: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/21.jpg)
Chapter 1 21
Bond Formation
• Ionic bonding: electrons are transferred.
• Covalent bonding: electron pair is shared.
=>
![Page 22: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/22.jpg)
Chapter 1 22
Periodic table
• Here He Beneath Blue Sea ©, Not• One Frigate Near. Na Might All Sinking• Poopdecks Shot Cleanly Away,
Potassium,Sodium• H He• Li Be B C N O F Ne• Na Mg Al Si P S Cl A• K Ca
![Page 23: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/23.jpg)
Chapter 1 23
Lewis Structures
• Bonding electrons
• Nonbonding electrons or lone pairs
Satisfy the octet rule! =>
C
H
H
H
OH
![Page 24: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/24.jpg)
Chapter 1 24
TIPS
• Neutral atoms Carbon 4 bonds (double bonds count as 2
triple bonds count as 3) and NO lone pairs. Nitrogen 3 bonds and one lone pair
Oxygen 2 bonds and two lone pairs BORON 3 bonds BUT no lone pairsOne who writes MORE than 3 bonds about a
neutral BORON is a MORON
![Page 25: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/25.jpg)
Chapter 1 25
C H-H+
CH- -
C+
N H-H+
N+ H+
N HH+
O
H-H+
O+H+
O
H+
H
TIPS2
![Page 26: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/26.jpg)
Chapter 1 26
Multiple Bonding
=>
![Page 27: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/27.jpg)
Chapter 1 27
EXAMPLES
CO2SO2 C2H3N
C3H6O isomer problem
![Page 28: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/28.jpg)
Chapter 1 28
Electronegativity and Bond Polarity
Greater EN means greater polarity
=>
![Page 29: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/29.jpg)
Chapter 1 29
C------Br C-------Li
C-------NBr--------Cl
EXAMPLES OF BOND POLARITY
![Page 30: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/30.jpg)
Chapter 1 30
Calculating Formal Charge
• For each atom in a valid Lewis structure:• Count the number of valence electrons• Subtract all its nonbonding electrons• Subtract half of its bonding electrons
C
H
H
H
C
O
O P
O
OO
O
3-
=>
![Page 31: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/31.jpg)
Chapter 1 31
EXAMPLES
C2H3O
HONH3
+
![Page 32: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/32.jpg)
Chapter 1 32
Ionic Structures
C
H
H
H N
H
H
H
+
Cl-
Na O CH3 or O CH3Na+
_
X
=>
![Page 33: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/33.jpg)
Chapter 1 33
Resonance - More than one Lewis Diagram
Example
C
O
C OH
H H
-1
Acetate ion
N
O
O
:
![Page 34: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/34.jpg)
Chapter 1 34
Resonance Example
• Consider writing Lewis structure for NO3-2
• The real structure is a resonance hybrid.• All the bond lengths are the same.• Each oxygen has a -1/3 electrical charge.
=>
N
O
OO
_ _
N
O
OO
_
N
O
OO
![Page 35: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/35.jpg)
Chapter 1 35
Must be legitimate Lewis structures
N
CH3
H3C
CH3
CH2+
-
N
CH3
H3C
CH3
CH2
NO NO Pentavalent nitrogen atom!!
Resonance Rules
![Page 36: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/36.jpg)
Chapter 1 36
• Only electrons can be moved (usually lone pairs or pi electrons).
![Page 37: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/37.jpg)
Chapter 1 37
Resonance structures?
N
O
O
: N
O
O
:
OK
CH
H
H
O
HCH
HOH
H
NO NO
![Page 38: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/38.jpg)
Chapter 1 38
Nuclei positions and bond angles remain the same.
C=C-C+ +C-C=C
CAN”T SAY “if you turn one around 180o you wouldEnd up with same structure”
Doing so would violate this rule
![Page 39: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/39.jpg)
Chapter 1 39
The number of unpaired electrons remains the same
H3C CH3..
H3C CH3
. .NO NO
![Page 40: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/40.jpg)
Chapter 1 40
DELOCALIZATION OF CHARGE USUALLY IS
STABILIZING
Delocalization of charge results in fractional chargesat alternate atoms
![Page 41: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/41.jpg)
Chapter 1 41
Major Resonance Form
• has as many octets as possible.
• has as many bonds as possible.
• has the negative charge on the most electronegative atom.
• has as little charge separation as possible.
Example
![Page 42: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/42.jpg)
Chapter 1 42
Major Contributor?
CH
HN
H
H
+C
H
HN
H
H
+
major minor, carbon does
not have octet.
=>
![Page 43: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/43.jpg)
Chapter 1 43
Other Examples
![Page 44: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/44.jpg)
Chapter 1 44
Chemical Formulas
• Full structural formula (no lone pairs shown)
• Line-angle formula
• Condensed structural formula
• Molecular formula• Empirical formula
CH3COOH• C2H4O2
• CH2O =>
C
H
H
H
C
O
O H
OH
O
![Page 45: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/45.jpg)
Chapter 1 45
BrØnsted-Lowry Acids and Bases
• Acids can donate a proton.
• Bases can accept a proton.
• Conjugate acid-base pairs.
CH3 C
O
OH + CH3 NH2 CH3 C
O
O-
+ CH3 NH3+
=>
acid base conjugatebase
conjugateacid
![Page 46: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/46.jpg)
Chapter 1 46
CH3CO2H+ :NH3 CH3CO2
- + NH4+
ACID
BASE
CONJ BASE
CONJ ACID
H3C
O:
OH+ H2SO4
H3C
OH
OH
++ -HSO4
Amphoterism - ability to behave as an acid or base
EXAMPLES
![Page 47: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/47.jpg)
Chapter 1 47
Acid and Base Strength• Acid dissociation constant, Ka
• Base dissociation constant, Kb
• For conjugate pairs, (Ka)(Kb) = Kw
• Spontaneous acid-base reactions proceed from stronger to weaker.
CH3 C
O
OH + CH3 NH2 CH3 C
O
O-
+ CH3 NH3+
pKa 4.74 pKb 3.36 pKb 9.26 pKa 10.64
=>
![Page 48: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/48.jpg)
Chapter 1 48
EXAMPLESWill NaOH neutralize phenol (C6H5OH)?
NaOH +
C6H5OH
HOH + C6H5ONa
pKa = 10 pKa = 15.7
_-OH
C6H5OH
HOH + C6H5O-+
YES!!
Weaker acidStronger acid
![Page 49: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/49.jpg)
Chapter 1 49
Determining Relative Acidity
• Electronegativity
• Size
• Resonance stabilization of conjugate base
=>
![Page 50: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/50.jpg)
Chapter 1 50
ElectronegativityAs the bond to H becomes more
polarized, H becomes more positive and the bond is easier to break.
=>
![Page 51: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/51.jpg)
Chapter 1 51
Size• As size increases, the H is more loosely
held and the bond is easier to break.• A larger size also stabilizes the anion.
=>
![Page 52: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/52.jpg)
Chapter 1 52
Resonance
• Delocalization of the negative charge on the conjugate base will stabilize the anion, so the substance is a stronger acid.
• More resonance structures usually mean greater stabilization.
CH3CH2OH < CH3C
O
OH < CH3 S
O
O
OH
=>
![Page 53: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/53.jpg)
Chapter 1 53
Lewis Acids and Bases• Acids accept electron pairs = electrophile
• Bases donate electron pairs = nucleophileCH2 CH2 + BF3 BF3 CH2 CH2
+_
nucleophile electrophile
=>
![Page 54: Chapter 11 ORGANIC CHEMISTRY STUDYOFCARBON -CONTAINING COMPOUNDS](https://reader035.vdocuments.us/reader035/viewer/2022081511/56649e995503460f94b9c936/html5/thumbnails/54.jpg)
Chapter 1 54
End of Chapter 1