Organic and Biochemistry organic chemistry: -- molecular shape is crucial 3-D structure of salicylic acid 3-D structure of acetylsalicylic acid ( a s p i r i n ) the study of carbon-containing compounds biochemistry: the chemistry of living things

Carbon is unique among the elements because: it can have up to four bonds per C atom--  single, double, or triple bonds it can form REALLY long chains of C atoms its bonds are strong –C–C– C=C –C=C–

Basic Definitions hydrocarbons: compounds containing only __ and __ alkanes:hydrocarbons having only ______ bonds single -- ALKANES = FUEL –C–C–C– –C– HH HHH H HH HH –C–C–C–C– HHHH HH HHHH HC -- very stable; no rxn w /acids, bases, strong oxidizers --–anes are saturated structural isomers: same molecular formula, different…bonding arrangements

alkenes: hydrocarbons having at least one ____ bond C=C alkynes: hydrocarbons having at least one ____ bond C=C H C H H HH H H–C–C=C–C–C–C–H H H HHH HHH CH 2 CHCH 3 CH 3 CC(CH 2 ) 2 CH 3 The simplest alkyne, ethyne (i.e., acetylene) – C 2 H 2 – is the fuel in oxyacetylene torches.

aromatic hydrocarbons: benzene and compounds w /a benzene-related structure -- –enes, –ynes, and aromatics are __________ unsaturated 6 C atoms in a planar ring w /“tweener” bonds (C 6 H 6 ) August Kekule (1829–1896), who claimed that a dream gave him insight into the structure of benzene.

“Finer-Point” Definitions Straight-chain compounds have… a single carbon backbone. Branched-chain compounds have… a main carbon backbone AND one or more branches Substituted compounds have… one or more H atoms removed, with other atoms in their place(s) (often halogens) Br CH 3 (CH 2 ) 3 CH 3 C 8 H 18 C 5 H 11 Br C 5 H 12 CH 3 CH 2 CH 2 CH 2 CH 3

Branches and H-replacing atoms/groups are collectively called… substituents. –C–C–C–C–C–C– H Cl HH H HH H HH Polyvinylchloride (PVC) is a material made of long-chain carbons that have many chloride substituents.

Functional group: a characteristic pattern that makes up a portion of a larger m’cule -- specific atoms, specific bonding arrangements -- importance: fgs largely determine the behavior of their m’cules –OH alcohols ketonescarboxylic acids –C– = O = O OH -- several examples of fgs: OO OH –COOH

Many organic compounds are combinations of several categories. Cl OH Cl O OH O Br C 6 H 11 Br Br sub. br. + sub. C 10 H 21 Cl fg + sub. C 6 H 13 OCl fg C 6 H 12 O 2 fg + sub. + br. C 9 H 17 OBr

Organic Nomenclature Memorize the prefixes that tell the # of C atoms in a chain. 1 = 2 = 3 = 4 = 5 = 6 = 7 = 8 = 9 = 10 = meth– eth– prop– but– pent– hex– hept– oct– non– dec– pent– non– dec– hept–

Naming Straight-Chain Alkanes 1. Find the longest continuous chain of C atoms. Choose the appropriate prefix. 2. The name ends with –ane. Provide the counterpart to the given. propane heptane (C 3 H 8 ) (C 7 H 16 )

Alkanes: modification for substituent hydrocarbon (HC) groups 1. Number the “longest chain” carbons. Start with the end nearest a branch. 2. Name and give the #ed location of each substituent. -- HC substituent groups use the prefixes, but end in –yl. 3. List substituents in alphabetical order. (i.e., branches)

Provide each counterpart. 4-ethyl-2-methylhexane octane ethyl-3-methyl (C 11 H 24 ) (C 9 H 20 )

Alkanes: modification for non-HC substituents 1. The “longest chain” MUST contain the substituent. -- example substituents: –NO 2 –NH 2 –F–Br–I nitroaminofluorobromoiodo 2. Number the chain carbons, starting with the end nearest a substituent. -- A non-HC substituent takes precedence over an HC branch. 3. Name and give the #ed location of each substituent. -- If necessary, choose #s so that their sum is as low as possible.

Provide each counterpart. 3-bromo-2-chlorohexane heptane 2-methyl-1-nitrobutane heptane 2-amino-6-nitro-3-propyl 2-ethyl-1,1-diiodo I I Cl Br NO 2 NH 2 NO 2

Alkanes: modification for cycloalkanes -- Use the cyclo- prefix before the word “alkane.” Provide each counterpart. 1-bromo-1-chloro-2-methylcyclopentane ethyl Br Cl (C 6 H 10 BrCl) (C 8 H 16 ) cyclohexane

Naming Alkenes and Alkynes 1. The C-chain MUST include the multiple bond. Use –ene or –yne, as appropriate. 2. Number so that you get to the multiple bond ASAP. -- The multiple bond takes precedence over branching or substituents. 3. Use di- or tri- right before –ene or –yne if you have two or three multiple bonds. Polyunsaturated fats and oils contain double and/or triple bonds.

Provide each counterpart. 1-butyne 2-butyne (C 4 H 6 ) (C 4 H 6 ) 7-methyl-2,4-nonadiene (C 10 H 18 )

7-fluoro-6-methyl-3-octyne Cl 3,3,4-trichlorocyclohexene F (C 6 H 7 Cl 3 ) (C 9 H 15 F)

4. For geometric isomers (different spatial arrangements of atoms), use cis- (same) or trans- (opposite). Geometric isomerism is possible only with… alkenes. Cl CH 3 CH 2 CH 2 CH 3 C=C Cl CH 3 CH 2 CH 2 CH 3 C=C hexene3-3,4-dichloro-trans- hexene3-3,4-dichloro-cis-

Benzene, Phenol, and Toluene These are the “Big Three” aromatic compounds. (“FEE nahl” or “fn AHL”) benzenephenoltoluene For phenols and toluenes, the C to which the –OH or –CH 3 is attached is carbon #1. CH 3 OH (C 6 H 6 ) (C 6 H 5 CH 3 )(C 6 H 5 OH)

Provide each counterpart. bromobenzene ethylbenzene 2-propylphenol Br OH (C 6 H 5 Br) (C 8 H 10 ) (C 9 H 12 O)

CH 3 I I 3,4-diiodotoluene OH NH 2 H2NH2N 2,6-diaminophenol CH 3 NO 2 O2NO2N 2,4,6-trinitrotoluene

ortho- para- dichlorobenzene meta- 1,2-dichlorobenzene Cl –Cl Cl –Cl 1,3-dichlorobenzene Cl 1,4-dichlorobenzene For this class, if a benzene ring is connected to an interior C atom in a hydrocarbon chain, it is called a phenyl (“FENN uhl”) group. It looks like THIS and has the formula… –C 6 H 5.

Provide each counterpart. 2-bromo-2-chloro-3-phenylpentane 3-nitro-2,4-diphenylhexane 3-amino-3-phenyl- ClBr NH 2 NO 2 1,1-dibromo-3-phenyl Br 1-butene cyclopentane

Alcohols Alcohols contain the hydroxyl group. Primary (1 o ) alcohols have one “R” group; secondary (2 o ) have two; tertiary (3 o ) have three. -- low molar mass alcohols are soluble in… polar solvents, due to the polar nature of –OH -- all alcohols have higher BPs than their parent alkanes (due to HBFs btwn. adj. m’cules’ OH grps) –OH –C– H OH – – R H –C– R OH – – R H –C– R OH – – R R

Naming Alcohols 1. Without being redundant, specify the location of the OH group(s); the suffix is –ol. 2. Use di- or tri- right before –ol if you have two or three OHs. 1-propanol 1,1-propane 3-ethylcyclohexanol 3-ethylphenol –OH Provide each counterpart. OH diol

5-bromo-2-propyl-6-chloro-1-hexanol HO– Br –Cl 1,2,4- HO OH triolcyclopentane Many pharmaceuticals (including aspirin, shown above) contain hydroxyl groups.

KetonesAldehydesEsters Carboxylic Acids Functional groups containing the carbonyl group Names end in –one, w /the C in the carbonyl having the lowest possible number. Names end in –al, w /the C in the carbonyl being C #1. The C in the carbonyl is C #1. Whatever is attached to the –O– is named first, then the name ends in –oate. Names end in –oic acid, w /the C in the carbonyl being C #1. –C– = O = O OH–C– = O H = O O–

Provide each counterpart. 3-hexanone 3-phenylbutanal 5,6-difluoro- O O O H O propyl O F F oatepropan 2-heptanone

2-ethyl 3-propylhexanoic acid -2-methyl 4,4,4-trifluorobutanoic acid O H O OH O O O F F F pentanal oate octanmethyl

Other Functional Groups to Recognize EthersAminesAmides (“EETH erz”)(“uh MEENZ”)(“uh MIDZ” or “AM idz”) –O– –N –C–N = O “caffe-ine”

Organic Reactions combustion of hydrocarbons OR compounds w /only C, H, and O: products are… CO 2 and H 2 O Write the equation for the complete combustion of 2-methyl-2-pentene. Write the equation for the complete combustion of ethylbutanoate.  C 6 H 12 + O 2 CO 2 + H 2 O 669 O O  C 6 H 12 O 2 + O 2 CO 2 + H 2 O 668

substitution: an H atom is removed and “something else” is put in its place -- In halogenation, a _______ atom replaces an H. halogen Write an equation for the reaction between ethane and chlorine. + Cl 2  –C–C–H HH H HH –C–C–Cl HH H HH + HCl If more chlorine is provided, the reaction will produce... AND SO ON. –C–C–Cl HH H HH + Cl 2  –C–C–Cl HH Cl HH + HCl

Substitution occurs with aromatic compounds, too. + Br 2 catalyst + CH 3 CH 2 Cl catalyst Br + HBr+ HCl Ethylbenzene is an important intermediate in the production of styrene which, in turn, is used to make polystyrene. Roughly 25 million tons of ethylbenzene are produced and used every year.

addition: a multiple bond is broken and two “things” are inserted (  (s) is/are broken,  remains intact) –C–C–Br HH Br HH –C–C–Br HH H HH –C–C–OH HH H HH + Br 2 H C=C H HH + HBr H C=C H HH + H 2 O H C=C H HH H 2 SO 4 H–C–C–C–C–H H H H H + Cl 2 –C–C=C–C– ClHH HH HH

A specific addition rxn is hydrogenation, in which __ is added across a multiple C-C bond. H -- requires a catalyst (usually a finely-divided _____) to rupture the multiple bond metal –C–C–H HH H HH + H 2 H C=C H HH catalyst Another addition reaction is polymerization. “lots” of ethylene H C=C H HH H H HH H H HH polyethylene –C–C–C–C– HH HH HH HH

condensation (or elimination, or dehydration): _____ is a product water -- One reactant provides an __, the other provides an ___. H OH CH 3 CH 2 OH + CH 3 OH NO 2 + H 2 O + HNO 3 H 2 SO 4 CH 3 CH 2 –O–CH 3 + H 2 O wateralcohol m’c an ether Complex protein molecules are made from condensation reactions of amino acids.

-- Condensation reactions polymerize amino acids into... proteins. H–N–C–C–OH OR” HH amino acid #1 H–N–C–C–OH OR’ HH amino acid #2 + H–N–C–C– OR” HH N–C–C–OH OR’ HH “a bit of a” protein + H 2 O water Note that amino acids have amine groups attached to the C NEXT TO the carboxyl group.

-- Amides can be formed in condensation rxns between carboxylic acids and amines. Write the equation for the reaction between butanoic acid and ammonia. O OH + NH 3 O NH 2 + H 2 O carboxylic acidamineamidewater Ammonia is the simplest amine.

Esterification is a condensation reaction between a carboxylic acid and an alcohol. Write the equation for the reaction between butanoic acid and 1-butanol. O OH HO + O O + H 2 O butanoate butyl (the active substance in the characteristic flavor/odor of pineapple)

Write the equation for the reaction between 3-phenyl-2-propenoic acid and ethanol. O OH HO + H2OH2O + -3-phenyl-2-propenoate (the active substance in the characteristic flavor/odor of cinnamon) ethyl (i.e, ethyl cinnamate ) “When in doubt, make water.” Mr. B O O