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Organic Chemistry
Organic Chemistry
- the study of organic compounds and their reactions,
properties, naming, structures and equations
Organic Compounds?
- Contain the element Carbon (C) and are held covalently.
2. Bonding
- Through covalent bonding
- Ionic compounds- for inorganic
3. Solubility
- If polar, soluble in H2O
- If nonpolar, then insoluble in H2O
5. Isomerism
- displayed by organic compounds
- a phenomenon where 2 or more compounds have the
same MF(Molecular Formula) but different in structures.
Example: Pentane
- (-ane : indicates that all bonds are single ( )
Gen formula: CnH2n+2
n= no. of Carbon
.. .. ..
•Single bond: H H H Br
.. : : Br
..
Br
..
:
:O O..:
•Double bond: ..
N N
•Triple bond: .. ..
Why UNEQUAL?
- Because atoms have different ElectroNegativity (EN)
. + . : :
S orbital S orbital
H H H. .H H H
2. Hybrid Orbitals
- Combination of Atomic Orbitals
-Stronger than AO
-No. of AO = No. of HO
Classes of Hybrid Orbitals
a. sp
b. sp2
c. sp3
Organic Chemistry MCL2018 12
Hybridization of Nitrogen
3
form four sp orbitals
• One sp orbital is occupied by
3
1. Bond Polarity
2. Bond Energy
3. Bond Length
4. Bond Angle
5. Bond Order
FC=O
FC = +1 bond is more polar, central atom is electron poor
a) CCl3H or b)CH3Cl?
HYDROCARBONS
C11= undec-
1. 11 carbon atoms (undecane) C11H24
C12= dodec-
2. 12 carbon atoms (dodecane) C12H26 C13= tridec-
3. 13 carbon atoms(tridecane) C13H28 C14= tetradec-
4. 20 carbon atoms (icosane) C20H42 C15= pentadec-
5. 21 carbon atoms (henicosane)C21H44 C16= hexadec-
C17= heptadec-
C18= octadec-
C19= nonadec-
C20= eicos-
Example: 3-methylpentane
How many are?
1. 1° C= 1. 1° H =
2. 2° C = 2. 2° H =
3. 3 °C = 3. 3° H =
CH3-CH2 – H = CH3-CH2–
ethane ethyl group
H2 C CH3 CH3
2. Number the chain from the end nearer to the first branch
H2 C CH3 CH3
H3C CH 2 CH CH 2 CH CH CH 2 CH3
H3C CH 2 CH CH 2 CH CH3
HC CH3 2
How many branches:____
CH3 Heptane
Parent:_________
H2 C CH3
H3C CH 2 CH CH 2 CH CH3
HC CH3 3
How many branches:____
CH3
Heptane
Parent:_________
1
1.
2.
CH3
CH3
CH3 CH CH CH3
1 2 3 4
Br NO2
1. 5-bromo-3-chlorohexane
2. 2 ethyl-5-isopropylhexane
• or
H2C CH 2
cyclobutane cyclopentane cyclohexane
cyclopropane
Note:
• Parent- is the cycloalkane
Isopropylcyclohexane
• No need to locate for the branch
• No need.
to number as well
H3C CH C CH CH 2 CH3
3-cyclopentyl-2,3,4-trimethylhexane
Ex:
1,4-dicyclohexylbutane
2. I
H3 C CH CH CH CH 2 Br
CH
H3C CH3
1-bromo-2-cyclopropyl-4-iodo-3-isopropylpentane
CH3
C C
H C C H
H H
• Note: notice that the double and triple bond are in C1 & C2
But-1-ene But-2-yne
H3C CH CH CH3 HC C CH2 CH3
But-2-ene
But-1-yne
Positional Isomers
What kind of isomers are they? _____________
H2C CH3
Name: 2-ethylpent-1-ene
Name: 4-ethyl-2-methylhex-3-ene
H3C CH 2 C C CH 2 CH3
H2C CH3
Cyclobuta-1,3-diene cyclobutadiene
Cyclopenta-1,3-diene cyclopentadiene
Cyclohexa-1,3-diene
Cyclohexa-1,4-diene
H3C CH 2
CH 2 CH3 CH3
CH 2
phenol
CH3
Benzoic acid styrene
SO3H
toluene NH2
X X
-Positional isomers
- use as common names
CN
NO 2
IN: 1-cyano-2-iodobenzene IN: 4-nitrophenol
CN: o-cyanoiodobenzene CN: p-nitrophenol
Br
NH2
IN: 2-bromotoluene
IN: 4-isopropylaniline
CN: o-bromotoluene
CN: p-isopropylaniline
IN: 1,2,4,5-tetramethylbenzene
H3C CH3
NO 2
1 CH3
IN:2,4,6-trinitrotoluene
O 2N 2 NO 2
H3CH 2C CH 2CH 3
I
CHO
CN
2. 5.
CH3
H3CH 2C CH 2CH 3
I Cl
COOH
3.
H3C NO 2
. phenyl
CH 2----- benzyl
1.
CH2 CH2 CH2 CH2------- 1,4-diphenylbutane
2. CH 2 CH CH2 3-phenylpropene
4. 1,2-diphenylcyclohexane
6 5 3-benzyl-6-phenylcyclohexene
1 4
2 3
CH 2
CH3
cyclobutyl alcohol
OH
OH
cyclopentyl alcohol
OH cyclohexyl alcohol
OH
H2C CH 2
Cyclohexane-1,2-diol
OH OH
OH
Ethane-1,2-diol OH
H3C CH CH2
Cyclohexane-1,4-diol
OH OH
OH
Propane-1,2-diol
H2C CH CH CH3
1. 3.
OH
but-3-en-2-ol cyclohex-2-enol
pent-3-yn-1-ol
O
Diphenyl ether Phenoxy benzene
OR Alkoxy branch
CH3O- methoxy
CH3CH2O- ethoxy
CH3CH2CH2O- propoxy
O-- phenoxy
IN: 1- methoxypropane OH
CH3
OCH2CH3 O O
IN: 2-ethoxypentane
IN:3,5-diphenoxytoluene
Organic Chemistry MCL2018 78
Nomenclature of Ethers
•. HO
H3CH 2CO O
OCH 3
6-ethoxy-3-methoxy-2-phenoxycyclohexanol
R C H R C R
R-CHO R-COR
R C H R C R
σ+ σ+
H C H H3C C CH3
IUPAC Name:
1
1. Count the # of carbon starting from the -CHO
2. Name the parent = as the name of the alkane with
ending e AL
OH
1. 6 5 3 2 1 Note: OH- hydroxy
H3C CH 2 CH CH CH 2 CHO
4
(Branch)
H2C CH3
3-ethyl-4-hydroxyhexanal
5 4 3 2 1
2. H3C CH CH CH2 CHO
pent-3-enal (No need to put 1 for CHO)
3. CHO
Benzaldehyde
IUPAC NAME:
1. Parent chain is the longest chain that passes through O
. C .
2. Name the parent= name of alkane w/ ending e change
into -one.
O
3. Start numbering at carbon nearer the . C .
H3C C CH 2 CH CH CHO
5-oxohex-2-enal
H3C C CH 2 C CHO
2,4-dioxopentanal
O O
H3C C CH 2 C CH3
Pentane-2,4-dione
H C CH 2 CH 2 C H
butanedial
-No need to locate because they are always on the two ends
O Cyclopentanone
OCH3
O Cyclohexanone
5-methoxycyclopent-2-enone
R C O H Or R-COOH
stabilized by resonance)
Oct-3-enoic acid
Pentanedioic acid
OCH3
4-hydroxy-3-methoxy-2-oxohept-5-enoic acid
COOH
Cyclopentane carboxylic acid
HOOC
..
..
O
..
R C NH2
1. Acid Amide
O
..
..
..
2. Ester R C O R
..
O
3. Acid Halides ..
R C X
.. ..
..
..
O O
..
..
4. Anhydride ..
R C O C R
..
ACETAMIDE ETHANAMIDE
2. CH3-CO-NH2
BUTANAMIDE
4. CH3CH2CH2-CO-NH2 BUTYRAMIDE
VALERAMIDE PENTANAMIDE
5. CH3CH2CH2CH2-CO-NH2
NH2
BENZAMIDE
-just memorize
• If N has
O a substituent:
CN: N-ethylacetamide
H3C C N CH 2CH 3
IN: N-ethylethanamide
2 1 H
CN: N-ethyl-N-phenylbutyramide
H3CH 2CH 2C C N
CH 2CH 3 IN: N-ethyl-N-phenylbutanamide
H3CH 2CH 2C C N
CN: N,N-diphenylbutyramide
IN: N,N-diphenylbutanamide
C N
IN: N,N-diphenylbenzamide
2. H3C C Cl
CN: acetyl chloride IN: ethanoyl chloride
O
-benzoyl chloride
Cl
R C O R
C O C Benzoic anhydride
O O
H3CH2CH2CH2C C O C CH2CH3
1 1
Alcohol
R C O OR
Acid
C O CH 2CH 3
ethyl benzoate
C O
phenyl benzoate
H3CH 2CH 2C C O
CN: phenyl butyrate
IN: phenyl butanoate
Kinds of Isomers:
1. Structural Isomers- different structure
2. Stereoisomers -same structure
- but different arrangement of atoms in
space
1. Chain Isomers-
- usually displayed by ALKANES & CYCLOALKANES.
- have same MF but different points of attachment
1. Conformational/Conformers
2. Geometric Cis/Trans Isomers
3. Optical Isomers
C C C C
b b b a
2 kinds of
Cis Trans atoms
Note: There should be 2 different atoms attached to the C with
double bond
1. but-2-ene
2. pent-2-ene
3. 1,2-dimethylcyclobutane
___1. 1-butene
___2. 1-chloropropene
___3. 2-hexene
___4.2-methyl-2-butene
C C C C
Cl Br Br H
H3C C CH2CH3
OH
H C OH HO C H
CH 2CH 3 CH 2CH 3
R & S System:
1. R - If priority groups decreases in clockwise
2. S - If priority groups decreases in counterclockwise
1. C C Cis-1,2-dichloroethene
Cl Cl
H Br
2.
C C Trans-1,2-dibromoethene
Br H
•Chemical
•1. Acidity
•2. Basicity
•3. Aromaticity
Types of IMFA?
1. Ionic/ Electrostatic Attraction
2. Dipole-Dipole Interaction
3. H-Bonding
4. LDF- London Dispersion forces
+ - + -
+ - + -
Examples of D-D:
• Carbonyl Compounds – contain carbonyl group
•Reciprocal H-Bond:
-a compound should have an H + and an atom with a LP.
Reciprocal - it can give and accept a H +
sp3
sp2
•Strength of H-Bond
- The more positive the H, the Stronger the H-Bond it
forms.
2. Boiling Point
- Temperature at which the vapor pressure of the liquid = to
the atmospheric pressure
- To boil: need to break the IMFA
3. Intramolecular H-Bond
- Presence of intra-molecular H-bond prevents it from
engaging in intermolecular H-bond IMFA, BP and MP
5. Symmetry
-Symmetrical molecule – are Nonpolar compounds
- NP; IMFA; BP and MP
>
Salts RCOOH> ROH> RNH2 > RCHO RCOR > ROR > R-H
LDF
Ionic H-bond Dipole-
dipole
O O H H O
H H H H H H
O
+
• II. Hydrocarbons
- IMFA: LDF
- Nonpolar; insoluble in H2O
- E.g. Hydrocarbons
R C O R C O
O R N
H > R > R R
> R
a) Polar Solvents O
O H3C CH2 OH
H3C CH2 OH C
H H H3C CH3
CH3
b) Non-polar solvents
CH3
CH 2 CH 2
Hexane
H3C O CH3
C C C C C OH Least Soluble
• MW ; Solubility in H2O
C C C OH C C C C C OH
MORE POLAR
6. Symmetry
- Symmetrical molecules are NP, insoluble in H2O
Acids Bases
1. HCl 1. NaOH
2. HNO3 2. NH4OH
O O
+
C H + O C O
H3C O H H H3C O-
+ H H
H
Cl H F
Strength of Acid
-depends on the tendency to lose the H+
2. The bulkier the -R, the stronger the e- release, the less +
the H
Ex. t-butyl alcohol and 1° alcohol
Cl-
H-Cl
Inc in acidity Inc stability of CB
Br-
H-Br
I-
H-I
..
NH2
..
< R NH2
N
H
..N H
N
..
O
R CH CH2
REACTIVE
SITES R C H
R C CH
σ+ O
σ-
R CH2 O H
R C R
σ+ σ-
R CH2 X
2 Kinds Reagents:
1. Electrophiles, E+ - e- loving reagent, e- poor
Electrophiles can be H+
1. + charge
Br – Br 2 Br
2. e- deficient, like Free radical
Cl
.
Fe Cl
3. Incomplete octet ex. lewis acid
Cl
X-
..
Ex. NH3
HO-
.. e- rich because of the LP
RO- H- O- H
.. ..
R O H
..
Ex. UV
A B .A + .B
E+ E+
A B A+ + :B-
CATION ANION
. . . .
H3C C CH3 H3C C CH3 H C CH3 H C H
- 3 Classes: 1 °, 2 °, 3 °
.. - .. - .. - .. -
H C H H C CH3 H3C C CH3 (CH3)C
H H H
1.
CH2 CH3
2.
H3C CH CH2 CH3
3. CH3
+ +
CH CH3 > CH2 CH2
3.
+ +
CH2 < CH 2
4.
2. Cl---Cl
3. H---O---H
4. H---NH2
5. HO—NO2
1. Addition Reactions
2. Elimination Reactions
3. Substitution Reactions
4. Acid-Base Reactions
. C . . C . . C C .
.
. .
4 max 3 groups 2 groups
groups (unsaturated) (unsaturated)
In Elimination:
1. Substrate is SATURATED
2. Product is unsaturated
•Reduction:
-Gain of e- (Inorg)
- Gain of H or loss of O or sometimes both (Organic)
- undergone by Oxidizing Agent
•Oxidation:
-Loss of e- (Inorg)- Inc in the oxidation num.
-Gain of Oxygen, loss of H or Both
- undergone by Reducing Agent
K2Cr2O7 K2Cr2O7
H3C CH2 OH
H2SO4 H2SO4
CH3
K2Cr2O7
H3C C OH No Reaction
H2SO4
CH3
- 3° OH cannot be oxidize
General Reaction: UV
R-H + X-X R-X + H-X
Alkane Halogen
UV
CH4 + Br2 CH3Br + HBr
1. Initiation- formation of X .
3. Termination
UV
H3C CH2 CH3 + Br-Br
More stable
2. UV
+ Cl2
3. H UV
+ Br2
CH3
4. UV
H3C CH2 CH CH3
+ Cl2
CH3
5. CH 2
UV
CH3 + Br2
Organic Chemistry MCL2018 191
REACTIONS OF UNSATURATED
HYDROCARBON
. .
Inc # of atoms bonded to C
C C + H+ Cl-
H H
A. Symmetrical B. Unsymmetrical
H3C CH CH2
H2C CH2
HC CH H3C C CH
CH3
H3C CH CH CH3
A. Symmetrical
Ex. 1) H2 in Pt or H2 in Ni or H2 in Pd
2) X2 in CCl4 (solvent) e.g Br2 in CCl4
B. Unsymmetrical
H-X (e.g.) H—Cl, H—Br, H—I
H—OH ; H—OSO3H (sulfuric) or H2SO4
•For Alkynes
-Change the bond into =, the = into –H H
H3C C CH+ H2 + Ni H3C C CH + H2 + Ni
H3C CH2 CH3
H3C C C H
Br Br
H Cl
symmetrical
H3C CH CH 2 H3C CH CH 2
Cl 1° 2°
H
Cl H
CH3 H CH3
Br H
CH3
3. Br2
H3C CH2 CH C CH3
CCl4
Pt
4.
H2
(excess)
(catalyst)
:
H
: OH
: O : H
H3C C C H H3C C C H
H H
C C H
H2SO4
C CH ENOL
+ H2O HgSO4
O H
C C H
HC CH
• Benzene ring: H H
- Aromatic
H H
- Resonance, 6 C’s are equivalent
6H’s are equivalent H H
Aromatic
- stable
Aromaticity is
preserved
1. Nitration +
Reagents: HNO3 + H2SO4 NO2 + HOH + HSO4-
2. Sulfonation: +
+
3. Halogenation:
Reagents: X—X + FeX3 X + FeX4-
5. Freidel-Craft’s Acylation
O O
Reagents:
R C X + AlX3 R C . + AlX4-
+
General Reaction:
H E
+ E+Nu- + H+Nu-
2. Br—Br + AlBr3
3. CH 2 Br + AlBr3
O
4. + AlCl3
C Cl
3. + HNO3 + H2SO4
5.
+ CH3Cl + AlCl3
CH 2 Br
AlBr3
6.
+ O
C Br
AlBr3
7.
+
Organic Chemistry MCL2018 213
REACTIONS OF ALCOHOLS
OH
c) [O]
NO RXN
R C R
H3C CH CH3
H2SO4 H3C CH CH2
σ β - H2O
OH
H3C CH 2 CH CH3
β σ β
H2SO4
CH3
HO H
H2SO4
HO
CH3
H2SO4
2. Nucleophile
- SN : Nu not involved in rate-determining step
1
-
2. Anhydride R C O C R
O
3. Esters
R C O R
O
O
4. Amide R C NH2
R C .
O
O-
R C L + H+Nu- R C L
Nu
+ -
R C Nu + H L
R C L + H+Nu-
NH3 H+ NH2-
-OR
-NH2
+
H3C C O- Na
O
CH3O-H (H+ OCH3)
H3C C Cl
+
H3C C O- Na
O
CH3O-H (H+ OCH3)
H3C CH 2 C Cl
HO-H
O O
CH3O-H
R C O C R
HO-H
O O
C O C
CH3O-H
(ammonolysis)
HO-H NaOH
+
R C O- Na
+ NH3
O (HCl)
C NH2
HO-H NaOH