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Organic Chemistry
1. Organic Chemistry - Organic chemistry is the study of carbon compounds. - The properties of organic compounds are determined by two factors: i. A molecular skeleton called a hydrocarbon. This is a series of carbon atoms linked together to form a stable framework that is almost completely unreactive. The unbonded electron positions are then filled (saturated) with hydrogen atoms. ii. A series of different reactive groups, called functional groups, can then be added. They determined the basic chemistry of the molecule. - Carbon atoms have unique properties that allow them to make many compounds: i. Carbon atoms can form four bonds ( C ) ii. They link together with covalent bonds to form chains and rings of different sizes, C C C C C C structural formula

Electron dot formula iii.

They form single, double and triple covalent bonds. C C C C C C C C C

- Hydrocarbons tend to have some unique properties that are determined by their covalent bonds: i. Hydrocarbons are easily decomposed by heat. ii. Hydrocarbons reactions are generally slow. iii. Most hydrocarbons are insoluble in water. Their molecules are nonpolar and are not attracted to the polar water molecules. 2. Alkanes a) Continuous Chain Alkanes - The simplest hydrocarbons are the alkanes that contain only hydrogen and carbon atoms with atoms with single covalent bonds. H H H C C H H H - The formula for and alkane can be given several ways: C5H12 (molecular formula) H H H H H 2C + 6H 1) H-C C C C C H H H H H H 2) CH3-CH2-CH2-CH2-CH3 (complete structural formula) (condensed structural formula or semi-structural)

3) C-C-C-C-C 4)

(skeletal structural formula) (line structural formula)

- The simplest alkanes form a chain. The first ten compounds in this homologous series are to be memorized: 1 CH4 Methane 2 C2H6 Ethane 3 C3H8 Propane 4 C4H10 Butane 5 C5H12 Pentane 6 C6H14 Hexane 7 C7H16 Heptane 8 C8H18 Octane 9 C9H20 Nonane 1 C10H22 Decane 0 Note: i. The names for the alkanes end in -ane. ii. The general formula for alkanes is CnH2n+2 b) Branched Chain Alkanes - Sometimes and atom or group of atoms can replace a hydrogen atom in an alkane. The added atom is called a substituent. CH3-CH2-CH3 CH3-CH(Br)-CH3 If the substituent is another hydrocarbon, it is called and alkyl group. CH3-CH2-CH3 CH3-CH(CH3)-CH3 An alkyl group (methyl) joined to the parent chain (propane) -When an alkyl group is attached to a parent chain, it creates a branched-chain alkane. The names of the alkyl groups are based on its alkane name but ending in yl. Examples: Methyl (-CH3) Ethyl (-CH2-CH3) or (-C2H5) Propyl (-CH2-CH2-CH3) or (-C3H7) Note: i. An alkyl group cannot exist by itself; it must be attached to some molecule. ii. The general formula for alkyl groups is CnH2n+1

3 Example: CH3-CH2-CH-CH2-CH3 CH2 CH2-CH3 This shows an ethyl group attached to a heptane molecule. The formula can also be given as CH3-CH2-CH(C2H5)-CH2-CH2-CH3 Nomenclature for Branched-Chain Alkanes 1. For One Branch 1. Find the longest chain and name it. 2. Number the carbons in order to locate the alkyl group. (Begin from the end that gives the branch the lower number). 3. The alkyl group name is placed in front of the parent chain name. 4. The number must be separated from the name with a hyphen. Example: CH3-CH2-CH2 CH-CH2-CH3 CH3 NAME: = 3 - methylhexane 2. For More Than One Branch - Each branch is again located on the main chain. - The branch names are listed alphabetically. - Prefixes are used if an alkyl group appears more than once. Example: CH3-CH2-CH2 CH-CH3 CH3-C-CH2-CH3 CH2-CH2-CH3 NAME: = 4,5-dimethyl, 4-ethyl- octane Note: i. Branches can be identified in condensed formulas by placing them in brackets. From the previous example (4-ethyl-4,5-dimethyloctane) CH3-CH2-CH2-CH(CH3)-C(CH3)(C2H5)-CH2-CH2-CH3 ii. Dont forget: Count from the end that gives the lowest numbers 2c) Structural Isomers - longest chain = octane - branches = methyl at 4 and 5 = ethyl at 4 - longest chain = hexane - branch name = methyl - branch location = 3rd atom

- It is possible to draw the structures of two or more hydrocarbons that have the same molecular formula but different structural formulas. These compounds are called structural isomers. C4H10 CH3-CH2-CH2-CH3 butane CH3-CH(CH3)-CH3 2-methylpropane

- Isomers will only be a different chemical only if they can be given a different name. - Isomers have different chemical and physical properties. Try This: 1. How many structural isomers are possible for each of the first five straight-chain alkanes. 2. Give the condensed structural formula and name for a) all of the isomers for C5H12 b) the five isomers of C6H14 3. Optional Challenge Name all 18 isomers of C8H18. 3. Alkenes and Alkynes - Remember that carbon can also form multiple bonds. Hydrocarbons containing a double bond are called alkenes ( C=C ). - Alkenes are unsaturated hydrocarbons because they contain fewer hydrogen atoms. These atoms were removed in order to create the double bond. - The other unsaturated hydrocarbon is the alkyne which contains a triple bond ( -CC- ). Nomenclature: 1. Find the longest chain containing the multiple bonds (Its name will now end in ene or -yne). 2. The main chain must now be numbered to give the multiple bonds the lowest number (instead of the branched chains). This number will be used in front of the name of the main chain. CH3-CH=C(CH3)-CH(CH3)-CH3 (3,4-dimethyl-2-pentene) CH3-CH2-CH(C2H5)-CCH (3-ethyl-1-pentyne) Note: i. The general formula for an alkene is CnH2n and for an alkyne is CnH2n-2. ii. The physical properties of the unsaturated substances are similar to those of the alkanes. iii. The most important difference in chemical properties is that multiple bonds are quite reactive. Try This: Name or provide the structural formula for these compounds:

5 i. ii. iii. iv. CH3-C(CH3)=CH-CH(CH3)-CH3 CH3-CH2-CH(C2H5 )-CCH 5,6-dimethyl-2-octyne 2-methyl-1-propene Summary Number of C 1 2 3 4 5 6 7 8 9 10 Name of the prefix for Meth Eth Prop But Pent Hex Hept Oct Non Dec Hydrocarbons molecule alkane CnH2n + 2 CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 Hydrocarbons molecule alkene CnH2n nil C2H4 C3H6 C4H8 C5H10 C6H12 C7H14 C8H16 C9H18 C10H20 Hydrocarbons molecule alkyne CnH2n -2 nil C2H2 C3H4 C4H6 C5H8 C6H10 C7H12 C8H14 C9H16 C10H18

4. Cycloalkanes (Geometric Shapes) - In some alkanes, the two ends of the chain have attached to form a ring. These are called cycloalkanes. Examples: 1) cyclobutane H2C CH2 H2C CH2 H2C or H2C C H2 Note: i. Cyclohexanes have only single bonds and that there general formula is CnH2n. Cycloalkenes and cycloalcynes also exist. ii. Cycloalkanes have strained bonds that lead to a less stable molecule than its equivalent alkane. Nomenclature: The ring carbons are numbered so as to give the substituents the lowest possible number (One substituent will always be 1). CH2CH3 CH2 or CH2 2) cyclohexane H2 C

6 CH3 CH3 1,3-dimethylcyclooctane 1-ethyl-2-methylcyclopropane

H3C

Try This: Give the structural formula for these compounds. a) 1-ethylcyclobutane b) 1,3-dimethylcyclopentane c) 1,1-dimethylcyclopropane d) cyclopropylcyclohexane (!) 5) Benzene - The most important group of cyclic hydrocarbons is the aromatic compounds, the simplest of which is benzene (C6H6). After benzene forms a ring, each carbon atom has one extra electron that is free to make half of a double bond. HC HC C H C H or CH CH HC CH CH C H C H

HC

The benzene ring can be shown as

Resonance occurs when two valid structures can be drawn for the same molecule. Resonance is the result of the combination of blending of the two possible structures. The actual substance is an average of all the possible arrangements. Molecules that exhibit resonance are very stable. Nomenclature: 1) One substituent Added: (branch) CH3 or C6H5(CH3)

Methylbenzene (or toluene) 2) When Used as a Substituent named phenyl (-C6H5) *(CnHn-1) CH3-CH-CH2-CH3 or CH3-CH(C6H5)-CH2-CH3

2-phenylbutane 3) Two Substituent Added (note the positions) H3C CH3 H3C CH3

H3C CH3

1,2-dimethylbenzene or o-dimethylbenzene (ortho position)

1,3-dimethylbenzene or m-dimethylbenzene (meta position)

1,4-dimethylbenzene or p-dimethylbenzene (para position)

Note: that one Substituent must be in the l position. 6 a) Fractional Distillation Directions: Use the key words and phrases with its matching step in the diagram to give a step-by-step explanation of the fractional distillation of oil. Tower a) Crude oil, fraction, alkanes b) Heater, 350oC, boiling point, vaporizing c) Bubble cap, rising gases, condensation, trays Fractions 1. 2. 3. 4. 5. 6. Residue, (tars, asphalt), highest boiling point (400oC), >C30 Lubricants and waxes, 3500C, approximately C20 C30 Heating/diesel oil, 250oC, C16 C20 Kerosene, 180oC, approximately C12 C16 Gasoline, 110oC, approximately C5 C12 Natural gases, lowest boiling points, C1 C4, LPG

6 b) Hydrocarbon Reaction 1. Cracking

8 Large fractions form the fractionation process is chemically broken with heat and a catalyst to produce more valuable fuel hydrocarbons with 5-12 carbon atoms per molecule. Large molecule small molecules Example: C17H36 C8H18 + C9H18 alkane alkene 2. Reforming This is the opposite of cracking. It can convert low-grade gasolines into higher grades with the use of heat and a catalyst. Small molecules large molecule Example: 2 C5H12(l) C10H22(l) + H2(g) 3. Combustion Most hydrocarbons are used as fuels (95%). Hydrocarbon + O2(g) CO2(g) +18H2O(g) + heat Example: 2C8H18 + 25O2 16CO2 + 18H2O + heat 4. Hydrogenation This process converts unsaturated hydrocarbons to saturated ones. Alkene + H2(g) alkane Alkyne + H2(g) alkene Example: CH2=CH-CH2-CH3(g) + H2(g) CH3-CH2-CH2-CH3(g) 1-butene butane

Try This: 1. Identify and complete each reaction. You must not break the Law (of Conservation of Matter) a) C14H30 into octane b) ethane into octane c) 1-octene into octane d) 1-octyne into octane 2. Show the complete combustion of: a) pentane b) hexane c) hexene 7. Functional Groups - The hydrocarbon skeleton of an organic molecule is chemically inert. Most organic chemistry, then, involves the atoms and molecules that are attached to this main chain. a) Structures - Functional groups are the atoms in an organic compound that have been added to a hydrocarbon chain. They are the only part of the molecule that is capable of reacting chemically. - Compounds are classified according to their functional groups. Since these groups can be attached to any chain, we will represent the inert hydrocarbon chain with R.

9 Family Name 1. Halocarbons 2. Alcohols 3. Ethers 4. Aldehydes Ketones 5. Carboxylic acids 6. Esters 7. Polymers Condensed Formula R(X) R(OH) R 1 O R2 R C(=O)H R1 C(=O) R2 R C(=O)(OH) R1 C(=O) O R2 ( - R 1 R2 - )n Example (3Cs) CH3-CH2-CH2(Cl) CH3-CH2-CH2(OH) CH3-O-CH2-CH3 CH3-CH2-C(=O)H CH3-C(=O)-CH3 CH3-CH2-C(=O)(OH) CH3-C(=O)-O-CH3 (-CH2-CH2-CH2-)n General Formula CnH2n+1X CnH2n+2O CnH2n+2O CnH2nO CnH2nO CnH2nO2 CnH2nO2

Questions: 1. Why does oxygen have to bond twice in a molecule? 2. How many times would these atoms bond? a) S b) Cl c) N d) F e) P 3. Which families cannot be made from methane? 4. Do any groups have the same general formula? b) Two Physical Properties - The presence of a functional group has a major effect on the physical properties of a compound. Intermolecular forces determine many physical properties, such as solubility and boiling point: - hydrocarbons have only weak dispersion forces. - functional groups may have strong hydrogen bonds. - Remember that hydrogen bonds are created between two molecules: - One molecule contains a hydrogen atom bonded to a highly electronegative atom (especially oxygen). These hydrogen atoms now can be considered to be a naked proton (+). - The other molecule will be polar with a - section (especially on oxygen). The hydrogen bonding, then, occurs between two highly polar molecules. - Boiling Points: Compounds with hydrogen bonding have higher than expected boiling points: at SATP, C2H6 = gas but CH3OH = liquid. - Solubilities: Compounds with hydrogen bonds are usually soluble in water (a polar molecule): C6H14 = insoluble in water but C5H11OH = soluble in water. Solubility decreases, as the molecule gets longer. (C12H25OH =slightly soluble in water). This is because the hydrogen bonding OH group has less effect on the larger molecule. 8. 1. Halocarbons (R X) - Halocarbons are produced by the substitution of a halogen (Family VIIA) for hydrogen in the hydrocarbon chain; Cl = chloro Br = bromo I = Iodo F = Fluoro

10 as well as NO2 = nitro NH2 = amino

Nomenclature: The halocarbon is treated as a substituent. Dont forget that substituents are named alphabetically. CH3-C(Br)(CH3)-CH3 2-bromo-2-methypropane CH3-CH(Cl)-C(NO2)(C2H5)-CH2-CH3 2-chloro-3-ethyl-3-nitropentane Try This: Name or provide the formula for the following: a) CH3-CH2(I) f) trichloromethane b) CH2(Cl)-CH2(Cl) g) 2-chloro-3-iodo-1-butene c) CH(F)(F)-CH(Cl)(Cl) h) 1,5-dinitro-2-pentyne d) CH3-CH2-CC-CH2(NH2) i) 1,3-difluorocyclopentane e) CH3-CH(NO2)-CH2(Br) j) 1,3-dibromo-3-phenylhexane Reactions: a) Addition Reactions A halogen (X) is added to an unsaturated hydrocarbon at the double/triple bond. These reactions are quite rapid because there are no strong covalent bonds to be broken. R1 = R2 + X2 RX RX Ethyne + chlorine gas 1,2-dichlorethane CHCH + Cl2 CH(Cl)=CH(Cl) which can be further reacted CH(Cl)=CH(Cl) + Cl2 CH(Cl)(Cl)-CH(Cl)(Cl) b) Substitution Reactions A halogen replaces hydrogen in a saturated hydrocarbon. These reactions occur quite slowly at room temperature because C H bonds are quite stable. R H + X2 R X + HX Ethane + chlorine chloroethane + hydrogen chloride C2H6 + Cl2 C2H5Cl + HCl More complicated molecules will form isomers. CH2(Cl)-CH2-CH2-CH3 + HCl CH3-CH2-CH2-CH3 + Cl2 CH3-CH(Cl)-CH2-CH3 + HCl c) Elimination Reactions This is the most common method for preparing alkenes. A halocarbon reacts with a hydroxide to produce an alkene. R R X + OH- R = R + H2O + XCH3-CH(Br)-CH3 + NaOH CH2 = CH-CH3 + H2O + NaBr 9. 2. Alcohols - Alcohols contain the hydroxyl (-OH) group: R O H

11 Nomenclatrue: Add -ol to the stem of the name of the parent chain. Number the position of the hydroxyl group. If more than one OH group is present, use these endings: - -diol (two hydroxyls) - -triol (three hydroxyls) Examples: CH3-CH(OH)-CH3 2-propanol CH3-CH(CH3)-CH2-CH2(OH) 3-methyl-1-butanol CH2(OH)-CH2-CH(OH)-CH3 1,3-butandiol Phenols are alcohols in which the OH group is attached to benzene. OH [C6H5(OH)] Try This: Name or give the formulas for the following: 1. CH3CH(OH)-CH3 5. 2-pentanol 2. CH2(Cl)-CH(OH)-CH3 6. 2,2,4-pentatriol 3. CH2(OH)-CH2(OH)-CH2-CH3 7. 3-ethyl-2-pentanol 4. C6H4(OH)(CH3) 8. 2-ethylphenol Reactions: 1. MAKING ALCOHOLS i. Fermentation producing ethanol from sugars by the action of yeast. C6H12O6(aq) 2CH3CH2OH(aq) + 2CO2(g) ii. Substitution the halogen in a halocarbon is replaced by a hydroxide. R X + M OH R OH + MX CH3-CH2(Cl) + NaOH CH3-CH2(OH) + NaCl iii. Addition a water molecule (H-OH) is combined with an unsaturated hydrocarbon. R1 = R2 + H OH R(OH) \ CH2=CH2 + H-OH CH3-CH2(OH) i. 2. REACTING ALCOHOLS Elimination Alcohols can be used to make alkenes when catalyzed by concentrated sulfuric acid
acid

R OH R1 = R2 + H OH CH3-CH2(OH) CH2=CH2 + H2O Properties: Alcohols tend to have high boiling points due to the strong hydrogen bonding that occurs between these molecules. - Smaller molecules are also soluble in water as they can hydrogen bond with the polar water molecules. - Longer chain molecules tend to be insoluble as the hydroxyl group has less effect on the molecule. They can be good solvents for nonpolar molecular compounds (like dissolves like).

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Try This: 1. Write a balanced equation for the following situations: a) reacting 2-iodopropane with Ca(OH)2 b) making 1-butene from 1-butanol c) making 1-propanol from propene 2. Why does wine bubble as it is fermenting? 10. 3. Ethers - These are compound in which oxygen is bonded between two carbon groups. O R1 Properties: Halocarbons Ethers Alcohols R2 Notice that this is actually a bent molecule.

Summary of Hydrogen Bonding

Hydrogen donor X X Hydrogen acceptor X Boiling point increases Solubility increases

Nomenclature: The two-alkyl groups are named in alphabetical order and followed by the word ether. CH3-CH2-CH2-O-CH3 CH3-CH2-O-CH2-CH3 methylpropyl ether diethyl ether Try This: 1. The molecular formula C3H8O can represent either two alcohols or an ether. Give their formulas and names. 2. Would an ether be soluble in a) a halocarbon? b) an alcohol? 11. 4. Aldehydes and Ketones - These two families share certain structural features and chemical properties. - They both contain the carbonyl group C = O, which we will show as (-C(=O)-) in O our condensed formulas. - Aldehydes = chain + carbonyl group + hydrogen = R C H O - Ketones = chain 1 + carbonyl group + chain 2 = Nomenclature: Aldhydes:O change the _e ending to _al HCH R 1 C R2

CH3-CH2-CH(=O)

13 methanal propanal

Ketones: count the total number of carbons present. Change the _e ending to _one. Number the carbonyl location. O CH3-C-CH3 propanone CH3-CH2-C(=O)-CH2-CH2-CH3 3- hexanone

Properties: - They have low boiling points because they have no O H bonds for hydrogen bonding. - When added to water, though, they can hydrogen bond to the water molecules so they are quite soluble in water. Try This: Draw and name the aldehyde and the ketone with the molecular formula of C4H8O. 12. 5. Carboxylic Acids - These organic acids contain the carboxyl functional group, -C(=O)-OH which include both the carbonyl group and the hydroxyl group. In molecular formulas, the carboxyl group is often presented as COOH. Properties: Carboxylic acids create the sour taste in foods and have distinctive odors. - They are polar molecules and are both hydrogen acceptors and hydrogen donors. Thus they will readily form hydrogen bonds, and smaller molecules are easily dissolved in water. - They have all of the properties of acids react with metals, make indicators change color, etc. Nomenclature: Replace the _e ending with _oic acid. structural Oformula CH3-CH2-C-OH propanoic acid molecular formula C2H5COOH condensed formula CH3-CH2-C(=O)-OH

Reactions: 1. Fermentation: glucose ethanol ethanoic acid (grape juice) (wine) (vinegar) 2. They undergo typical acid reactions (neutralization, for example) but at a slower rate.

Try This: 1. Name a) CH3-CH2-CH2-C(=O)OH b) CH3-C(CH3)(CH3)-C(=O)OH c) COOH 2. Give the formula for a) hexanoic acid b) 3-methylpentanoic acid 3. Use the example to write a balanced equation for the organic reaction: a) KOH + HCl KCl + HOH

14 KOH + CH3-COOH ? b) 2Na + 2HCl 2NaCl + H2 Na + CH3COOH ? 13. 6. Esters (Acid + Alcohol Ester) - Esters are derivatives of carboxylic acids in which the OH of the carboxyl group has been replaced by an OR from an alcohol. O R1-C or R1COOR2 or R1-C(=O)-O-R2 O-R2 Reactions: Esters are prepared by combining a carboxylic acid with an alcohol in a process called esterification: O O R1-C + HO-R2 R1-C + HOH OH O-R2 carboxylic acid alcohol ester water Nomenclature: The name of an ester has two parts: i. Locate the alcohol branch and name it as an alkyl group. ii. Locate the acid branch. The ending of the acid name is changed from _oic acid to _oate O alcohol acid CH3-C CH3-CH2-C(=O)-O-CH2-CH3 O-CH3 methyl ethanoate ethyl propanoate Properties: -Esters are odor chemical (fruits and flowers). - are added to foods to enhance taste + odor. Try This: Give the esterification reaction (with formulas and names) for i. Propanoic acid and butanol ii. Butanoic acid + propanol iii. Ethanol and methanoic acid 14. 7. Polymerization - A polymer is a giant molecule formed by the covalent bonding together of repeating smaller molecules called monomers. .. + monomer + monomer + .. polymer - One method of creating these polymers by addition polymerization the joining together of unsaturated (multiple bond) monomers. If A = the monomer, the polymer will appear as -A-A-A-Acatalyst

15 n CH2=CH2 (-CH2-CH2-)n ethane (ethylene) polyethylene n CH3CH=CH2 (-CH2(CH3)-CH2-)n propene (propylene) polypropylene - A condensation polymer is formed by reacting two different compounds together. In order to do this, a small molecule (usually water) must be split off from the functional groups. If A = first monomer and B = second monomer, then the polymer will appear as -A-B-A-BHere is a general example: HO-X-OH + HO-Y-OH (-O-X-O-Y) + 2H2O di acid or di alcohol Note: polyethylene = ice cream plastic containers, polypropylene = nylon rope
catalyst

Try This: Write the formula for the following polymers, which were formed by addition polymerization. 1. Polyvinyl chloride (PVC) which is made form chloroethane. 2. Teflon which is made form tetrafluoroethene.