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Aliphatic Functional Groups to Know and Love

Common Aromatic Compound Names

Nomenclature Roots Meth- (Me)/Form- : -CH3 Eth- (Et)/AcetProp- (Pr) But- (Bu) PentHexHepOctNonDecUndecDodecTridecTetradecPentadecHexadecHeptadecOctadecNonadecEicosTriacontTetracontPentacontDecacont: -CH2 CH3 : -CH2 CH2 CH3 : -CH2 CH2 CH2 CH3 : -CH2 CH2 CH2 CH2 CH3 : -CH2 CH2 CH2 CH2 CH2 CH3 : -CH2 CH2 CH2 CH2 CH2 CH2 CH3 : -CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3 : -CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3 : -CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3 : -CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3 : -CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3 : -C13H27 : -C14H29 : -C15H31 : -C16H33 : -C17H35 : -C18H37 : -C19H39 : -C20H41 : -C30H61 : -C40H81 : -C50H101 : -C100H201

Structural Formulas

Molecular Formula A count of each atom type. Molecular formulas can represent multiple compounds. Ex: C2H4O

Kekule Structures Structures that show the position of every atom and bond.

Condensed Structures Structures that group functional groups together.

Alternatively:

What about larger compounds? Line structures Structures where carbons are represented by ends and corners unless otherwise indicated. Hydrogens bonded to carbons are implied. All other atoms are shown.

Alkanes (C-C)
Saturated hydrocarbons Each carbon has the maximum number of hydrogens present. Formula:

Unsaturated hydrocarbon: At least one carbon has fewer than the maximum number of hydrogens allowed.

Properties of Alkanes Intermolecular Forces:

Polarity:

Boiling Point:

Solubility:

Acidity/Basicity:

Hybridization and VSEPR Geometry:

Valence Bonds:

Isomers Different molecules with the same molecular formula.

Constitutional Isomers Isomers that differ in connectivity. C4H10:

C5H12:

Degree of Branching

Primary carbons (1o) will have ____ bonds to a carbon. Secondary carbons (2o) will have ____ bonds to carbons. Tertiary carbons (3o) will have ____ bonds to carbons. Quaternary carbons (4o) will have ____ bonds to carbons. These are rarely reactive.

In the case of double and triple bonds, each pi bond counts as one bond.

Functional groups will adopt the degree of branching of the carbon they are bonded to.

In the molecule below, circle the 2o carbon(s). Box the 3o carbon(s). Draw an arrow to the 4o carbon(s). Dont disturb the 1o carbon(s).

Alkane Nomenclature 1. Identify the largest continuous chain of carbons. This is called the parent chain.

2. If there are two series of carbon of the same length, rings take priority over chains.

3. Identify the substituents and number the carbons on the parent chain so that the substituents have the lowest possible numbering.

If the substituent is a carbon chain, name it as a parent chain and replace ane with yl.

4. List substituents alphabetically. Ignore prefixes.

5. Replicated substituents are grouped together using di-, tri-, tetra-, penta-, hexa-, hepta-, etc. The prefix is not used to alphabetize substituents.

6. Common substituents: OH = hydroxyl NH2 = amino CN = cyano

Cl, Br, F = chloro, bromo, fluoro NO2 = nitro

Name the following compound:

Cycloalkanes
Cycloalkanes have the same properties as alkanes. The formula of a basic cycloalkane is:

Angle strain The energetic resistance of bond angles to deviate from their VSEPR angles

Cyclopropane and Cyclobutane: High angle strain = unstable sp3-hybridized carbons prefer _______ bond angles Planar or puckered (cyclobutane only) conformations (3-D geometries)

Cyclohexane: The angles of a regular hexagon are _______; therefore, cyclohexane will prefer to adopt a 3-D shape to minimize angle strain.

________ conformations are the _______ stable conformations of cyclohexane. Cyclohexane can have ___ two possible conformers of this type that can interconvert between each other.

Axial sites - __________ to the cyclic plane, alternate up and down. Substituents in the axial position make the cyclohexane ______ stable. Equatorial sites - __________ to the cyclic plane, alternate up and down. Substituents in the equatorial position make the cyclohexane ______ stable.

Label the sites below as axial or equatorial.

Why are conformers with substituents in the equatorial position more stable?

Steric hindrance When the size of a large substituent competes for space with an adjacent group. This can lead to limited chemical reactivity and instability

t-butylcyclohexane

Substituent in axial position

Substituent in equatorial position

Dash ( Wedge ( paper

) indicates atoms going ________ or ________ the plane of paper ) indicates atoms going ________ or ____________ the plane of

Two substituents are ______ to each other when they are going in the same directions. They are ______ to each other when they are going in different directions.

Draw planar representations of the two molecules above.

Out of all cycloalkanes, cyclohexane will experience the least strain in its bonds; smaller cycloalkanes will suffer from angle strain, and larger cycloalkanes will experience strain from steric hindrance of its substituents.

Bicyclic molecules Molecules with two rings that share a side

Spiro molecules Molecules with two rings that share an atom

Bridged molecules Molecules with three rings that share two atoms with each other

Heterocyclic molecules Molecules with a ring in which a carbon has been replaced with any non-carbon atom.

Classify the following molecules:

Alcohols and Alkyl Halides (R-CH2-OH)/(R-X)


Properties of alcohols/alkyl halides: Intermolecular Forces

Polarity

Boiling Point

Solubility

Acidity/Basicity

Hybridization

Nomenclature For alcohols, list the group as a substituent or use the alcohol as part of the parent name by replacing the last e with ol.

For alkyl halides without hydroxyl groups, list the group as a substituent or replace the ane of the parent chain with yl, then replace the ine of the halogen with ide.

A special note on alcohols: _____ alcohols can oxidize to aldehydes, while _____ alcohols can oxidize to ketones.

Random fact: heating an alcohol in the presence of a strong acid will produce an alkene. Such types of reactions where alkenes are formed from taking out two substituents on adjacent carbons are termed ________________ reactions. For example:

Stereochemistry

Stereoisomers Compounds with the same formula, constitution, and functional groups in the same place but have a different orientation in space

A molecule is termed __________ when it isnt superimposable on its mirror image. The center of stereochemistry is typically ______ -hybridized. Typically, but not always, a molecule will be chiral if a carbon has _____ different substituents bonded to it

Enantiomers Two molecules that are mirror images of each other but are not super-imposable

In an achiral environment, enantiomers will behave identically and have the same physical properties except for their rotation of ____________________________.

Racemic mixture: a ________ mixture of two enantiomers. These will not rotate light.

Molecules that rotate light clockwise are termed dextrorotatory and are indicated by a (+) in front of their name. Molecules that rotate it counterclockwise are termed levorotatory and are indicated by a (-) in front of their name.

Enantiomers can also be named with the R/S or E/Z systems. Names are determined based on the molecular masses of substituents and their spatial arrangement relative to each other.

Finally, they can be named with the L/D system, where the name of the compound is determined based on whether the compound forms from the L or D enantiomer of glyceraldehyde.

Diastereomers two stereoisomers that are not mirror images to each other. These have at least ____ chiral centers

Alkenes (C=C)

Formula:

Properties Hybridization:

Valence Bonds:

All other properties are similar to those of ________________.

Nomenclature Name the alkene like you would an alkyl chain, but drop the ane and add ene. The parent chain must contain the double bond. Be sure to indicate which number carbon starts the double bond.

Vinyl alkenes, or terminal alkenes, have a double bound at the end of a chain. Allyl alkenes have a double bond at a 2-carbon. Note: alkenes dont necessarily have to be either vinyl or allyl.

Indicate which of the above alkenes are vinyl or allyl.

In alkanes, carbon-carbon sigma bonds can rotate freely. However, alkenes cant rotate due to the necessity of massive energy to break pi bonds. This introduces the possibility of ________________ isomers.

When the two heaviest substituents on opposite carbons in a double bond are on the same side of the double bond, _________ or ______ is written before their names. If they are on opposite sides and are diagonal to each other, _________ or ______ is written before their names. In general, the _______ isomer of an alkene will be more stable than the _______ isomer.

Fun fact: alkenes are popular compounds for undergoing ____________________ reactions, where the double bond is broken by adding a substituent to each sp2hybridized carbon of the said pi bond. Three of many types of these reactions are given below:

Formula-

Properties Acidity/Basicity

Hybridization

Valence Bonds

All other properties are similar to those of _______________________________.

Nomenclature Name the alkyne like you would an alkene, except replace ene with yne.

An alkyne that has the formula RC2H is classified as _______________ alkynes. All others are _________________ alkynes.

Acidity of terminal alkynes

Protons on terminal alkynes are more easily extracted than those on alkenes and alkanes because the triple bond has _______________ character.

Dienes

A diene is an alkene with ______ carbon-carbon double bonds.

____________ diene a diene with double bonds that act independently of each other. The double bonds are always at least ______ carbons away from each other.

____________ diene a diene with double bonds _______ carbon away from each other. The pi electrons delocalize*, making the diene very _____________.

____________ diene a diene where a carbon atom has _____ double bonds. The pi bonds are perpendicular to each other and require a lot of energy, making the diene very _____________.

*In organic chemistry, electron delocalization will always lead to compound and ion stability. These electron delocalizations always occur within the pi orbitals and can occur in compounds with adjacent double bonds or with a series of adjacent pi bonds and electric charge, radical electrons, or lone pairs. These structures will always have multiple resonance structures. In other words, compounds that show resonance have electron delocalization, which stabilizes them.

Diels-Alder Reaction

A ______________ diene will react with an______________, in this case termed a ______________, to form a ___________________.

Cycloalkenes Cycloalkenes are carbon rings that include one double bond between two carbons in the ring. Their general formula is _____________________. These cycloalkenes dont undergo conjugative delocalization of pi electrons and thus dont exhibit resonance (such structures are discussed in the next section.

Aromaticity

Compounds are said to be _______________ when it contains a conjugated ring of delocalized pi electrons that increase the stability of the compound. (It will thus show resonance)

A special note on benzene After experimentation, August Kekule determined the following in relation to benzene: 1. Benzenes molecular formula is C6H6 2. All the hydrogens on benzene are equivalent 3. The octet rule requires that there be four bonds to each carbon Kekule then hypothesized the following structures for benzene:

However, a flaw was soon discovered in the structure. Kekules structure suggests that the following compounds would have different properties:

The structure implies that a single bond connects the carbons of two substituents in one isomer and a double bond connects the carbons in the second. However, no such cases of isomerism were known, and none could be found. Kekule therefore proposed that two isomers could exist but interconverted too rapidly to be noticed:

We know that this isnt the case. Experiments show that all of the carbon-carbon bonds in the ring are energetically equivalent and have a bond length of 140 pm, exactly halfway between the sp2-sp2 double bond length of 134 pm and the sp2-sp2 single bond length of 146 pm.

The two structures correctly show the arrangement of atoms, but they differ in the placement of electrons. Thus, they are resonance structures, and neither shows the correct bonding of benzene by itself. We therefore know that the hybrid structure of benzene has the following appearance:

The bond angles in benzene are _________, the angles of a regular hexagon. Since ________-hybridized atoms prefer these angles, benzene will remain planar instead of twisting into a 3-D shape like cyclohexane. Furthermore, the conjugative delocalization of pi electrons enhances benzenes stability to such a degree that the bonds within the ring all act together as one functional group instead of six separate bonds.

A Demonstration of Aromatic Stability Cyclohexanol Deprotonation -

Phenol Deprotonation -

Nomenclature In monosubstituted benzene derivatives, if using benzene for the parent chain, treat substituents like you would with an alkane.

If using benzene as a substituent, name it a phenyl (Ph) group.

If using benzene attached to one carbon, name it a benzyl (Bz) group.

For disubstituted benzene derivatives, use ortho- or o- if the substituents are next to each other, meta- or m- if the substituents are separated by a hydrogen, and para or p- if the substituents are on opposite ends of the ring.

For trisubstituted derivatives and above, use the numbering system.

Refer to the table of benzene derivatives at the beginning of this packet for more common benzene derivatives.

Friedel-Crafts Alkylation/Acylation Alkylation:

Acylation:

Ethers (R-O-R)

Properties of Ethers Intermolecular Forces:

Polarity:

Boiling Point:

Solubility:

Acidity/Basicity:

Hybridization and VSEPR Geometry:

Valence Bonds:

Compound

Structural Formula

Dipole Moment (D) 1.3 0 1.69

Boiling Point (oC) -24 -42 78

Dimethyl ether CH3OCH3 Propane CH3CH2CH3 Ethanol CH3CH2OH

Solubility in H2O (g/100 mL) 0.071 0.004 Miscible

Nomenclature If naming the ether as a substituent, take the smaller chain attached to the oxygen, replace ane with oxy, and add the name of the parent chain after it.

If naming the ether as a functional group, replace the ane of the side chains with yl, write them alphabetically, and add ether. If both side chains are the same, write di and then the side chain once before writing ether.

Cyclic Ethers and Epoxides The carbons attached to the ether oxygen can be bonded to other chains that form a ring. These ethers are called cyclic ethers. Example: Tetrahydrofuran (THF)

Epoxides are a special type of cyclic ethers where the carbons bonded to the ether oxygen are also bonded to each other. Epoxides tend to be ____________ because of ____________________. Example: oxirane, 1,2-epoxycyclohexane

Aldehydes and Ketones (RH=O)/(RR=O)

Properties of Aldehydes and Ketones Intermolecular Forces:

Polarity:

Boiling Point:

Solubility:

Acidity/Basicity:

Hybridization and VSEPR Geometry:

Valence Bonds:

Nomenclature For aldehydes, name the compound like you would an alkyl chain and replace the ane with al.

For ketones, name the compound like you would an alkyl chain and replace the ane with one.

If a compound contains both an aldehyde group and a ketone group, the aldehyde takes priority. Use oxo- to name the ketone group substituent.* Be sure to mark the # carbon the ketone is on.

*Something useful to know: any C=O group is called a ________________ group.

Aldehydes and ketones will oxidize to ____________________ and ___________ respectively. They will reduce to _________________________ and ________________________ respectively.

Carboxylic Acids and Esters (RCOOH)/(RCOOR)

Properties of Acids and Esters Intermolecular Forces:

Polarity:

Boiling Point:

Solubility:

Acidity/Basicity:

Nomenclature For carboxylic acids, name the acid like you would an alkyl chain, then drop the ane and add -oic acid.

For esters, list the chain bonded to the oxygen as a substituent, then name the parent like you would an alkyl chain. Replace the e on the end of the parent chain with oate.

Carboxylic acids and esters will reduce to ______________ and _______________ respectively.

Fischer Esterification Perhaps the most common way to prepare esters is through the Fisher Esterification, which involves an equilibrium reaction between a carboxylic acid and an alcohol. Note: the acid will retain both of its oxygens and lose only the

proton bonded to the second oxygen, while the alcohol will lose its hydroxyl group.

Saponification- KNOW THIS Although soap has many ingredients that contribute to its properties, the main active molecule involves an anion with a polar carboxylate head and a nonpolar fatty acid tail bonded to a sodium or potassium cation. The structure of the sodium salt is displayed below:

Common carboxylate salts:

When in water, these sodium/potassium salts dissociate. The nonpolar fatty acid tails of the carboxylates are hydrophobic and thus prefer to bond intermolecularly with other fatty acids, forming a sphere coated with polar heads and filled with fatty acid tails. These spheres are termed micelles.

We use soap to wash our skin because nonpolar compounds on our skin wont bond to the water and fall off due to strong intermolecular forces. When we scrub soap on our skin, the micelles break, and the fatty acid tails bond to the nonpolar substances. The micelles re-form with the unwanted residue trapped inside, and the polar heads hydrogen-bond with water to carry the substances away.

Whether sodium or potassium is used to make the soap does have an effect on the product. In general, a sodium salt will produce solid soap, which will be treated with further chemicals to form a bar. A potassium soap will typically be liquid, which will be treated to form a soap gel.

Fatty acids are normally found in the form of triglycerides instead of monomers. In the laboratory, saponification typically occurs by reacting a vegetable oil, a reliable source of triglycerides, with sodium hydroxide in the presence of water, ethanol, and heat. Sodium hydroxide by itself is a caustic solid and must be dissolved with water to react. In addition, triglycerides do not dissolve in water, limiting the saponification reaction to the surface, so ethanol is added to dissolve the triglyceride into the aqueous solution. Finally, saponification is an endothermic reaction and requires an external source of heat for the reaction to occur. The basic chemical reaction for in-lab sodium saponification is displayed below:

Amines

Properties of Amines Intermolecular Forces:

Polarity:

Boiling Point:

Solubility:

Acidity/Basicity:

Hybridization and VSEPR Geometry:

Nomenclature There are two ways to name amines where the nitrogen is bonded to only one carbon (primary amines): in the alkanamine system, take the parent chain, drop the last e, and add amine. In the alkylamine system, replace the ane of the parent chain with yl and add amine to the end. Remember to denote the location of the amine with numbering in both cases. Note: amines bonded to phenyl rings are called anilines.

Other amines are named as N-substituted derivatives of primary amines. The parent chain is taken to be the one with the longest carbon chain. Rings, however, take precedence over chains.

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