Organic Chemistry

Hybrid orbitals are orbitals used to describe bonding that is obtained by taking combinations of atomic orbitals of an isolated atom

In the case of Carbon, one s orbitals and three p orbitals, are combined to form 4 sp3 hybrid orbitals The carbon atom in a typical sp3 hybrid structure has 4 bonded pairs and zero unshared electrons, therefore, tetrahedral structure AXaEb (a + b) 4 + 0 = AX4 The four sp3 hybrid orbitals take the shape of a tetrahedron

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Organic Chemistry
Shape of sp3 hybrid orbital different than either s or p

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Carbon Geometry
The combination of single, double, and triple bonds in an organic molecule will determine the molecular geometry sp3 Tetrahedral AX4 sp2 trigonal planar AX3 sp linear AX2 sp linear AX2

Review Chapter 11 Multiple bonding in carbon compounds

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Hydrocarbons

Compounds containing only C and H Saturated Hydrocarbons: Alkanes only single () bonds Unsaturated Hydrocarbons:

Alkenes

Alkynes

Double (=) Bonds Triple () bonds Aromatic Hydrocarbons (Benzene rings) (6-C ring with alternating double and single bonds)

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Hydrocarbons

Alkanes (Aliphatic Hydrocarbons)

Normal-chain: linear series of C atoms C-C-C-C-C-C-

Branched-chain: branching nodes for C atoms

Methyl Propane

Cycloalkanes: C atoms arranged in rings

Cyclohexane
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Hydrocarbons

Alkanes: CnH2n+2

Straight Chained Alkanes

H H C H H H H C H H C H H C H H

Methane
H H

Propane
H
H

H C

H C

H C H
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C
H

C
H

C H

Ethane
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Butane

Hydrocarbons

Molecular Formulas of n-Alkanes

Methane: Ethane: Propane: Butane: Pentane: Hexane: Heptane: Octane: Nonane: Decane:

C-1: C-2: C-3: C-4: C-5: C-6: C-7: C-8: C-9: C-10:

CH4 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 CH3CH2CH2CH2CH3 CH3(CH2)4CH3 CH3(CH2)5CH3 CH3(CH2)6CH3 CH3(CH2)7CH3 CH3(CH2)8CH3
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Hydrocarbons
Straight Chain (n) Alkanes

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Nomenclature of Alkanes

Determine the longest continuous chain of carbon atoms. The base name is that of this straight-chain alkane. Any chain branching off the longest chain is named as an alkyl group, changing the suffix ane to yl For multiple alkyl groups of the same type, indicate the number with the prefix di, tri, Ex. Dimethyl, Tripropyl, Tertbutyl The location of the branch is indicated with the number of the carbon to which is attached Note: The numbering of the longest chain begins with the end carbon closest to the carbon with the first substituted chain or functional group
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Hydrocarbons

Alkenes

When a Carbon atom forms a double bond with another Carbon atom, it is now bonded to 2 other atoms instead of 3 as in an Alkane The Geometry now changes from 4 sp3 orbitals (Tetrahedral AX4E0) to 3 sp2 hybrid orbitals and 1 unhybridized 2p orbital (AX3E0 Trigonal Planar) lying perpendicular to the plane of the trigonal sp2 hybrid orbitals
Review Chapter 10 - Geometry
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Hydrocarbons

Alkenes Two sp2 orbitals of each carbon form C H sigma () bonds by overlapping the 1 s orbitals of the two H atoms The 3rd sp2 orbital forms a C-C () bond with the other Carbon A Pi () bond forms when the two unhybridized 2p orbitals (one from each carbon) overlap side-to-side, one above and one below the C-C sigma bond A double bond always consists of 1 and 1 bond

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Hydrocarbons

Alkenes: CnH2n Alkenes substitute the single sigma bond () with a double bond a combination of a sigma bond and a Pi () bond
The

double-bonded (-C=C-) atoms are sp2 hybridized The carbons in an Alkene structure are bonded to fewer than the maximum 4 atoms Alkenes are considered: unsaturated hydrocarbons H H H H C C C C H H H CH3
Ethene or Ethylene
Propene
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Hydrocarbons

Molecular Formulas of Alkenes

Ethene: Propene:

CH2=CH2 CH2=CHCH3

Butene: Pentene: Decene:

CH2=CHCH2CH3 CH2=CHCH2CH2CH3 CH2=CH(CH2)7CH3

Conjugated Molecules
Alkene (or aromatic) with alternating Sigma bonds and Pi bonds) Ex. 2,5-Dimethyl-2,4-Hexadiene CH3CH3=CH-CH=C(CH3CH3)

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Hydrocarbons

Alkynes General Formula - CnH2n-2 The Carbon-Carbon (-C-C-) bond is replaced by a triple bond Each Carbon of an Alkyne structure (-CC-) can only bond to one other Carbon in a linear structure Each C is sp hybridized (sp linear geometry) Alkyne compound names are appended by the suffix yne The electrons in both alkenes (-C=C-) and alkynes (-CC-) are electron rich and act as functional groups Alkenes and alkynes are much more reactive than alkanes
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Hydrocarbons

Alkynes

Ethyne
H C C H

or

Acetylene
H C C CH3

Propyne
A Terminal Acetylene

H3C

CH2

CH2

CH3

3-Hexyne
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Aromatic Hydrocarbons

Aromatic Hydrocarbons are Planar molecules consisting of one or more 6-carbon rings
Although often drawn depicting alternating and bonds, the 6 aromatic ring bonds are identical with values of length and strength between those of C-C & C=C bonds The actual structure consists of 6 bonds and 3 pairs of electrons delocalized over all 6 carbon atoms

The bond between any two carbons resonates between a single bond and a double bond
The orbital picture shows the two lobes of the delocalized cloud above and below the hexagonal plane of the bonded carbon atoms

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Aromatic Hydrocarbons
Molecular Orbitals of Benzene

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Aromatic Hydrocarbons
H H C C H C H C C C H H H H H C H

C
C C H

C
C H

benzene

benzene

Condensed Resonance Form of Benzene

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Functional Groups

Oxygen containing functional groups:

alcohols, ethers, aldehydes, ketones, esters, carboxylic acids, anhydrides, acid halides

Nitrogen containing functional groups:

amines, amides, nitriles, nitro

Compounds containing Carbonyl Group (C=O)

acids, esters, ketones, aldehydes, anhydrides, amides, acid halides

Compounds containing Halides

alkyl halides, aryl halides, acid halides

Compounds containing double & triple bonds

alkenes, alkynes, aryl structures (benzene rings)

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Functional Groups

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Functional Groups

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Alcohols

Functional Groups with only single bonds An alcohol, general formula R-OH, is a compound obtained by substituting an -OH group for an H atom in a hydrocarbon

primary alcohol: one carbon attached to the carbon with the OH group secondary alcohol: two carbons attached to the carbon with the OH group tertiary alcohol: three carbons attached to the carbon with the OH group

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Alcohols
CH3 CH2 CH2 OH Propanol (n-propyl alcohol) t-butanol sec-butanol (primary alcohol) (tertiary alcohol) (secondary alcohol)

Alcohol Nomenclature Drop final e from hydrocarbon and add suffix ol

OH CH3CH2CH2CH2CH3 CH2CH2CH2CH3 CH3

4,6-dimethyl-3-octanol (a secondary alcohol)

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Alcohols

Alcohol Reactions Alcohol structure similar to water (R-OH vs H-OH) Alcohols react with very active metals to release H2

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Alcohols form strongly basic Alkoxide (R-O-) Ions High melting points and boiling points of alcohols result from Hydrogen Bonding Alcohols dissolve Polar molecules Alcohols dissolve some salts

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Aldehydes and Ketones

Aldehydes

In Aldehydes the Carbonyl group always appears at the end of a chain Butanal (Butyraldehyde)

Aldehyde names drop the final e from the alkane names and -al Propanal, Isobutanal, etc. Alternate naming conventions:

Benzaldehyde, Propionaldehyde
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Aldehydes and Ketones

Ketones The Carbonyl Carbon always occurs within a chain as it is bonded to two other Alkyl groups (R, R)

Ketones are named by numbering the carbonyl C, dropping the final e from the alkane name, and adding -one, 4-Heptanone 4-Heptanone (Dipropylketone) Alternate naming conventions: Use the Alkyl root and add ketone Methylisopropylketone (3-methyl-2-butanone)

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Aldehydes and Ketones

Like the C=C= bond, the carbonyl C=O bond is electron-rich Unlike the C=C= bond, the C=O bond is highly polar

A - The and bonds that make up the CO bond of the carbonyl group B - The charged resonance form shows that the CO bond is polar (EN = 1.0)
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