Organic Chemistry

Chapter 20 - Organic Chemistry


20.1 - Hydrocarbons



Organic Chemistry

The study of molecules containing C along w/ other elements (H, O, N, etc). Organic chemicals can either be synthetic/natural, harmless/harmful.


They can be represented in different ways


Alkanes [Saturated Hydrocarbons]

  • Consist of all single covalent bonds between C atoms, all C atoms in alkanes have sp3 hybrid orbitals which are bonded to four other atoms (C/H)

    • Since all alkanes: consist of C & H atoms, similar bonds, structures, & formulas; CnH2n+2

    • C chains have zigzag structure b/c of the bond angles being ~109.5º

    • Often drawn as a skeletal structure (line-angle structure) in which C atoms are not drawn


The base names come from the # of C:


Groups that come off the main chain (substituents) are named by changing the “ane” ending above to “yl”, for e.g. the -CH3 group is the methyl group. When the group has 3+ C, different shapes are possible.


Types of Carbons


Procedure in Naming Linear Alkanes*

  1. Find the longest C chain [gives base name]

  2. # the C in the longest chain to give any substituents the lowest # if same, alphabetical order

  3. Names & give the # of each substituents

    1. 2+ substituents present [indicate w/ prefix   i.e. di, tri]

    2. List in alphabetical order, ignore prefixes, not iso

* Rules change when functional groups +’ed refer to section on alkynes


Nomenclature of Alkynes [Naming System]

  • Contains a C-C triple bond, has suffix “yne”

    • Procedure is similar to alkanes but triple bond must be a part of longest C chain used for the base name

      • Position of triple bond is indicated by # & should be as low as possible, true for all functional groups [structures w/ more than C & H atoms]


Nomenclature of Alkenes 

  • Contains a double bond, has suffix “ene”

    • The procedure for naming alkenes is the same as that of alkynes

  • Double bonds do not rotate, results in geometric isomers [componds w/ same molecular formula & groups bonded to another but different spatial arrangements of these groups]

Cahn, Ingold & Prelog Rules

  • Used to identify which groups have priority in alkenes w/ many substituents

    • > Priority groups are on the same side of the double bond [Z isomer]

    • > Priority groups are on opposite sides of the double bond [E isomer]

  1. > atomic # = > priority   e.g. Br > Cl

  2. If the groups start w/ the same atom, move out along the chain to find the first difference 



Nomenclature of Chiral Molecules

  • If a molecule can be superimposed on its mirror image [achiral], if not [chiral]

    • Shortcut in 1110: look for a C w/ 4 different groups attached





Enantiomers

  • They have all the same physical properties (m.p, b.p, solubility, density) & react the same way w/ achiral chemicals



R & S Configurations

  • The two possible configs. At C are specified using Cahn, Ingold & Prelog rules

    • Priority is assigned to each of the groups & the lowest priority group is oriented away from the viewer

    • R config. (rectus/right) if arrow drawn from the highest priority to second is clockwise

    • S config. (sinister/left) if counterclockwise




























20.2 & 20.3 - Alcohols,  Ethers, etc.



Nomenclature of Other Functional Groups


Alcohols 

  • Have a -OH group on a C

  • Suffix “ol”

    • Can form hydrogen bonds, thus have relatively high bps.


Aldehydes 

  • Have a C-O double bond & have H off the C

  • Suffix “al” always ends a chain thus assigned to C1 1 not written


Ketones 

  • Have a C-O double bond & two C off the C

    • Suffix “one” to indicate location of C-O double bond


Carboxylic Acids

  • Have a C-O double bond & an OH group off C

    • Suffix “oic acid”

    • Starts chain [linear carboxylic acids] thus 1 not written

    • Are weak acids & can hydrogen bond


Esters

  • Have a C-O double bond & an O w/ C attached to it

    • Suffix “oate” 

    • The part attached to O is named like a substituent 


Halogens 

  • Contains: F, Cl, Br, I

    • Are named as substituents and the # of every halogen must be given in the name












Chapter 3 - Conformation and Stereochemistry


3.1 - Conformations of Open-Chain Organic Molecules



Stereochemistry

A branch of chemistry that studies the different spatial arrangements of atoms in a molecule

  • Cis/trans isomerism

  • Chair/boat conformations


Conformations and Conformational Isomer (Conformer)

Different spatial arrangements of atoms in a molecule result from σ bond rotation are called conformational isomers (conformer) in organic chemistry



Newman Projection

A convenient drawing convention is used to visualize different conformations of a molecule better


we look lengthwise down a specific bond of interest – in this case, the carbon-carbon bond in ethane. We depict the ‘front’ atom as a dot, and the ‘back’ atom as a larger circle

 

Bonds are NOT represented by dashed/wedges



Types of Isomerism

  • Conformational 

  • Constitutional 

  • Different

  • Enantiomers (Optical)

  • Identical 

  • Geometric

Conformational

Different conformations of the same molecule result from rotation around a single bond






Staggered vs. Eclipsed Conformations




Staggered conformation is where the molecule is in the lowest energy conformation because the distance between the front and back C-H bonds are maximized giving it the most stable conformation. DA = 60º


Eclipsed conformation is where the molecule is in the highest energy conformation. DA = 0º


The dihedral angle [DA] refers to the distance between the front & back carbon (eg. the angle formed from the front C-H bond and the back one).





Notice that although they are staggered, the two methyl groups are not as far apart as they could be. Is called gauche conformation.




Anti conformation, where the two methyl groups are positioned opposite each other DA = 180º





Steric strain, which is the repulsive interaction caused by the two bulky methyl groups being forced too close together.








3.2 - Conformations of Cyclic Organic Molecules


Cyclic organic molecules = cyclo, many of which are aromatic, thus planar


[Cis] 2 substituents on the same ring are both pointing towards the same side of the ring


[Trans] Opposite sides 




Ring structures in organic molecules are usually 5-6 membered. 3-4 membered rings are sometimes found in nature but are significantly > in energy, thus are unstable due to angle strain; the 4 bonds around the sp3 hybridized C are forced out of their preferred tetrahedral angles.