3. Organic Compounds: Alkanes and Cycloalkanes

Based on McMurry’s Organic Chemistry, 8th edition, Chapter 3

Families of Organic Compounds

! Structural features that make it possible to classify compounds by reactivity are call functional groups ! Organic compounds can be grouped into families by their common structural features ! Chapter 3 deals with structure of some common functional groups but emphasizes alkanes and alkane isomers ! Alkanes are compounds that contain only carbons and hydrogens, all connected exclusively by single bonds

3.1 Functional Groups

! A functional group is a collection of atoms at a site within a molecule with a common bonding pattern ! The group reacts in a typical way, generally independent of the rest of the molecule ! For example, a double bond in simple and/or complex alkene reacts with bromine in the same way; see below

Br Br CH CH CH3 CH3 3 3 Br2

starting material

Br2

Br starting material Br 3

Survey of Functional Groups

! Know Table 3.1 which lists a wide variety of functional groups (also inside back cover) ! As you learn about them in each chapter and in laboratory (i.e., the FTIR experiment, page63), it will be easier to recognize them ! The functional groups affect the reactions, structure, and physical properties of every compound in which they occur ! Know your MANTRA when I say, “reaction”

Types of Functional Groups: Multiple Carbon–Carbon Bonds ! *Alkenes have a C=C double bond ! *Alkynes have a C÷C triple bond ! *Arenes have special bonds that are represented as alternating single and double C-C bonds in a six- membered ring ! The arene shown is conjugated ! - " - !

Functional Groups with Carbon Singly Bonded to an Electronegative Atom

! *Alkyl halide: C bonded to halogen (C-X) ! * Alcohol: C bonded O of a hydroxyl group (C-OH) ! * Ether: Two C’s bonded to the same O (C-O-C)

! * Amine: C bonded to N (C-NR2; where R=H or C) ! Thiol: C bonded to SH group (C-SH) ! Sulfide: Two C’s bonded to same S (C-S-C) ! Bonds are polar, with partial positive charge on C (#+) and partial negative charge (#$) on electronegative atom; remember F O N Cl Br I S C H

Groups with a Carbon–Oxygen Double Bond (Carbonyl “C=O” derivatives) ! *Ketone: two C’s bonded to the carbonyl, C=O ! *Aldehyde: one hydrogen bonded to C=O ! *Carboxylic acid: %OH bonded to the C=O ! *Ester: C-O bonded to the C=O, watch the video, “additional words about the esters” ! Amide: C-N bonded to the C=O ! Acid halide: X bonded to the C=O ! Carbonyl C has partial positive charge (#+) ! Carbonyl O has partial negative charge (#-).

amide

ester

3.2 Alkanes and Alkane Isomers

! Alkanes: Compounds with C-C single bonds and C-H bonds only (no functional groups) ! Connecting carbons can lead to large or small molecules ! The formula for an alkane with no rings in it must be CnH2n+2 where the number of C’s is n ! Alkanes are saturated with hydrogen (no more can be added ! Catentation -the formation of networks (often “chains”) of identical atoms bond together

Names of Small Hydrocarbons

Possible alkane isomers No. of Carbons Formula Name (CnH2n+2) “catenation”

1 methane CH4 1

2 ethane C2H6 1

3 propane C3H8 1

4 butane C4H10 2

5 pentane C5H12 3

6 hexane C6H14 5

7 heptane C7H16 9

8 octane C8H18 18

9 nonane C9H20 35

10 decane C10H22 75

10 20 isocane C20H42 366,319

Constitutional Isomers

! Same molecular formula, different structure to be isomers ! Isomers that differ in how their atoms are arranged in chains are called constitutional isomers ! Compounds other than alkanes can be constitutional isomers of one another

Alkane “Constitutional” Isomers

! Constitutional Isomers - Same formula different

structure; C5H12

n-pentane 2-methylbutane 2,2-dimethylpropane

! straight-chain (continuous-chain) or normal alkanes

n-pentane 2-methylbutane 2,2-dimethylpropane ! branched-chain alkanes

! 12 n-pentane 2-methylbutane 2,2-dimethylpropane

Condensed Structures of Alkanes

! A condensed structure does not show bonds but lists atoms, such as isomers of pentane

! CH3(CH2) 3CH3 (n-pentane)

! (CH3) 2CH2CH2 CH3 (2-methylbutane)

! CH3C(CH3)2CH3 (2,2-dimethylpropane)

n-pentane 2-methylbutane 2,2-dimethylpropane

3.3 Alkyl Groups

! Alkyl group – remove one H from an alkane (a part of a structure) ! General abbreviation “R” (the “rest” of the molecule and should be defined, for example, R=H, CH3) ! Name: replace -ane ending of alkane with -yl ending _ ! CH3 is “methyl” (from methane, Me-) _ CH2CH3 is “ethyl” (from ethane. Et-) ! See Table 3.4 for a summary of the above

Abbreviations

You must know your abbreviations: Me, methyl group Et, ethyl group n-Pr, i-Pr for the two propyl groups •n-Pr, normal straight chain propyl •i-Pr, isopropyl (branched) Four butyl groups (common names) n-Bu, sec-Bu, i-Bu, t-Bu n-butyl, sec-butyl, isobutyl, t-butyl

Special positions (handed out in class)

Types of Bond Positons

! Know your Bond Positions ! a carbon at the end of a chain (primary alkyl group) ! a carbon in the middle of a chain (secondary alkyl group) ! a carbon with three carbons attached to it (tertiary alkyl group)

1° 2° 3° 4°

Practice problem

! Draw all isomers for C6H14; give their line- angle formulas & bond positions, 1°, 2°, 3° ! Identify all primary, secondary, tertiary centers by writing in 1°, 2°, 3° next to each carbon 1° 2° 2° 2° 1° 2° 2° 1° 2° 1° 3° 3° 1° 2° 2° 1° 1° 1° 1° 1° 3° 1° 3° 4° 2° 1° 1° 1° 1° 1°

This problem may be turned in, so do it an place it in your portfolio

! Draw all fourteen isomers for C5H12O ! give their line-angle formulas. ! Identify all primary, secondary, tertiary centers by writing in 1°, 2°, 3° next to each carbon ! In each isomer, circle and name each alkyl branch attached to an oxygen atom. ! For example 2° 1° 1° 2° 1° O butyl methyl Called methyl butyl ether

The answer is linked on the bond position web page.

Additional practice problems

3.4 Naming Alkanes (IUPAC)

! Compounds are given systematic names by a process that uses ! Prefix-Parent-Suffix ! Due Process follows specific rules ! Circle longest continuous chain ! Number to the closest branch ! If two possibilities-chose one with more branches ! Carbons in that chain are numbered in sequence ! Substituents are numbered at their point of attachment ! Complex substituents are named as compounds would be ! See specific examples in text

Good practice problems

The IUPAC rules can be very complex, but each organic compound can be assigned a unique name, and from the name the structure can be written.

Many organic compounds are known by their common or trivial name – especially if they are complex. These frequently give no clue as to the structure.

Listening for endings, like, -ol for alcohol, -one for ketone, -al for aldehyde, -ane for alkane, -ene for alkene, -yne for alkyne, alkyl -ate for ester are helpful in identifying the major functional group in a molecule 23

3.5 Properties of Alkanes

! Called paraffins (low affinity compounds) because they undergo few types of reactions

! Complete combustion produces CO2 carbon dioxide, water, and heat

! They react with Cl2 in the presence of light to replace H’s with Cl’s (not controlled)

Physical Properties

! Boiling points and melting points increase as size of alkane increases ! Forces between molecules (dispersion and induced temporary dipoles if cooled & compressed) are weak

3.6 Cycloalkanes

! Cycloalkanes are alkanes that have carbon atoms that form a ring (called alicyclic compounds) ! Simple cycloalkanes rings of %CH2% units, (CH2)n, or CnH2n ! Structure is shown as a regular polygon with the number of vertices equal to the number of C’s (a projection of the actual structure)

cyclobutane cyclopentane cyclohexane cyclopropane

Complex Cycloalkanes

! Naturally occurring materials contain cycloalkane structures ! Examples: chrysanthemic acid (cyclopropane), prostaglandins (cyclopentane), steroids (cyclohexanes and cyclopentane)

Properties of Cycloalkanes

! Melting points are affected by the shapes and the way that crystals pack so they do not change uniformly

3.7 Naming Cycloalkanes

! Count the number of carbon atoms in the ring and the number in the largest substituent chain. If the number of carbon atoms in the ring is equal to or greater than the number in the substituent, the compound is named as an alkyl-substituted cycloalkane ! For an alkyl- or halo-substituted cycloalkane, start at a point of attachment as C1 and number the substituents on the ring so that the second substituent has as low a number as possible. ! Number the substituents and write the name ! See text for more details and examples

Good practice problems

3.8 Cis-Trans Isomerism in Cycloalkanes

! Rotation about C-C bonds in cycloalkanes is limited by the ring structure ! Rings have two “faces” and substituents are labeled as to their relative facial positions ! There are two different 1,2-dimethyl-cyclopropane isomers, one with the two methyls on the same side (cis) of the ring and one with the methyls on opposite sides (trans)

&, Beta (top) above face

', alpha (bottom) below face

Stereoisomers

! Compounds with atoms connected in the same order but which differ in “fixed” three-dimensional orientation, are stereoisomers ! The geometric isomer terms “cis” and “trans” should be used to specify stereoisomeric ring structures ! Recall that constitutional isomers have atoms connected in different order

&, Beta (top) above face

', alpha (bottom) below face

Good practice problems