opyright Goalby Bancroft's School rganic: module 4 revision guide ydrocarbon is a compound consisting of hydrogen and carbon only Basic definitions to know Saturated: ontain single carbon-carbon bonds only Unsaturated: ontains a = double bond Molecular formula: The formula which shows the actual number of each type of atom Empirical formula: shows the simplest whole number ratio of atoms of each element in the compound General formula: algebraic formula for a homologous series e.g. n2n Structural formula (displayed formula): show all the covalent bonds present in a molecule omologous series are families of organic compounds with the same functional group and same general formula. They show a gradual change in physical properties (e.g. boiling point). Each member differs by 2 from the last. same chemical properties. Functional groupis an atom or group of atoms which when present in different molecules causes them to have similar chemical properties Drawing Displayed formulae When drawing organic compounds add the hydrogen atoms so that each carbon has 4 bonds Remember that the shape around the carbon atom is tetrahedral and the bond angle is 109.5 o General rules for naming carbon chains ount the longest carbon chain and name appropriately Find any branched chains and count how many carbons they contain Add the appropriate prefix for each branch chain Eg - 3 methyl or - 2 5 ethyl 3 7 propyl code no of carbons meth 1 eth 2 prop 3 but 4 pent 5 3,5-dimethyl heptane hex 6 hept 7 oct 8 non 9 dec 10 When compounds contain more than one functional group, the order of precedence determines which groups are named with prefix or suffix forms. The highest precedence group takes the suffix, with all others taking the prefix form. owever, double and triple -bonds only take suffix form. rder of priority highest first: arboxylic acids >carboxylic acid derivative>nitriles>aldehydes>ketones>alcohols>amines
opyright Goalby Bancroft's School homologous series alkenes functional group prefix / suffix (* = usual use) suffix -ene example alcohols suffix* -ol prefix hydroxy- haloalkanes halogen prefix chlorobromoiodo- l aldehydes suffix -al prefix formyl- ketones suffix* -one prefix oxo- carboxylic acids suffix -oic acid nitriles suffix -nitrile prefix cyano- amines suffix* -amine prefix amino- 2 2 esters -yl oate Acyl chloride -oyl chloride 3 l l Amide -amide 3 2 2 Acid Anhydrides R 3 R 3 2
General rules for naming functional groups The functional group is indicated by a prefix or suffix. e.g. chloroethane The position of the functional group is given by a number counting from the end that gives the functional group the lowest number. (for aldehydes, carboxylic acids & nitriles, the functional group is position 1). 4 3 2 1 2-bromobutane We only include numbers if they are needed. methyl propane 2 l 2 dichloromethane Where there are two or more of the same groups, di-, tri- or tetra are used and. Words are separated by numbers with dashes If there is more than one functional group/substituent, numbers are separated by commas and the groups are listed in alphabetical order (ignoring di, tri, etc.). 3 3 3 2 l 2 2 3 2 l 2 3 2,3-dibromo-2-methylbutane. 2,2-dibromo-1-chlorobutane. 3-bromo-1-chlorobutane The suffix for alkenes can go in front of other suffixes. 2 l= 2 2-chlorobut-3-en-1-ol aloalkanes lass the halogen as a substituent on the chain and use the suffix -fluoro, -chloro, -bromo, or iodo. (Give the position number if necessary: 4 3 2 1 2-bromobutane Alcohols These have the ending -ol in place of the last -e, and if necessary the position number for the group is added between the name stem and the ol 3 2 3 1 2 3 4 Butan-2-ol If the compound has an group in addition to other functional groups that need a suffix ending then the can be named with the prefix hydroxy-): 3 2-hydroxypropanoic acid Aldehydes An aldehyde s name ends in al It always has the = bond on the last carbon of the chain so it does not need an extra number arboxylic acids These have the ending - oic acid in place of the last -e, but no number is necessary for the acid group as it must always be at the end of the chain. The numbering always starts from the carboxylic acid end opyright Goalby Bancroft's School Ethanal Ethanoic acid Ketones Ketones end in -one When ketones have 5 s or more in a chain then it needs a number to show the position of the double bond. E.g. pentan- 2-one The prefix oxo- should be used for compounds that contain a ketone group in addition to a carboxylic acid or aldehyde Propanone 3 2-oxopropanoic acid If there are carboxylic acid groups on both ends of the chain then it is called a - dioic acid Ethandioic acid
opyright Goalby Bancroft's School Amines These end in amine. There is, however, rather confusingly two ways of using this suffix. The exam board tend to use the common version where then the name starts propylamine. The IUPA version of the same chemical is propan-1-amine. If the amine is secondary and has two alkyl groups attached to the nitrogen the each chain is named 2 propylamine r propan-1-amine 3 2 2 3 -methylbutylamine r -methylbutan-1-amine If there is another functional group as well as the amine group then the prefix amino is used. 3 2 3 2-aminopropanoic acid. 2 23 Diethylamine r -ethylethanamine itriles These end in ile, but the of the group counts as one of the chain. ote the stem of the name is different to : butanenitrile and not butannitrile. butanenitrile 3 3 2-hydroxy-2-methylpropanenitrile arboxylic acid derivatives Esters Esters have two parts to their names The bit ending in yl comes from the alcohol that has formed it and is next to the single bonded oxygen. The bit ending in anoate comes from the carboxylic acid. (This is the chain including the = bond) methylpropanoate Acid Anhydrides This is called ethanoic anhydride. It is ethanoic because it is two ethanoate groups joined together.. 3 3 If the groups are different then each one is named e.g. ethanoic propanoic anhydride 3 3 2 Acyl hlorides Take the carboxylic acid name, remove the oic acid bit of the 3 name and replace by oyl l chloride ethanoyl chloride 3 3 3 l 2-methylpropanoyl chloride Amides Take the carboxylic acid name, remove the oic acid bit of the name and replace by amide 3 2 ethanamide Secondary and tertiary amides are named differently to show the two (or three) carbon chains 3 2 -methyl propanamide 3 3 2 3 3,-dimethylpropanamide 3 3 3 3,,2-trimethylpropanamide 4
opyright Goalby Bancroft's School Isomers Structural isomers: same molecular formula different structures (or structural formulae) Structural isomerism can arise from hain isomerism Position isomerism Functional group isomerism hain isomers: ompounds with the same molecular formula but different structures of the carbon skeleton pentane 2-methylbutane 2,2-dimethylpropane position isomers: ompounds with the same molecular formula but different structures due to different positions of the same functional group on the same carbon skeleton 1-bromopropane 2-bromopropane Functional group isomers: ompounds with the same molecular formula but with atoms arranges to give different functional groups ethanol: an alcohol Methoxymethane: an ether yclohexane- cyclo alkane 3 2 2 2 = 2 hexene- alkene Stereoisomerism Stereoisomers have the same structural formulae but have a different spatial arrangement of atoms There are two types of stereoisomerism: geometrical (EZ isomerism) and optical isomerism Alkenes can exhibit a type of isomerism called E-Z stereoisomerism E-Z isomers exist due to restricted rotation about the = bond Single carbon-carbon covalent bonds can easily rotate E-Z stereoisomers arise when: (a) There is restricted rotation around the = double bond. (b) There are two different groups/atoms attached both ends of the restricted double bond
opyright Goalby Bancroft's School Z- but-2-ene two different groups attached either end of the restricted double bond- leads to EZ isomers But-1-ene two identical groups attached to one end of the restricted double bond no E-Z isomers E -but but-2-ene These are two isomers as the lack of rotation around the double bonds means one cannot be switched to the other But-1-ene is a structural isomer of But-2- ene but does not show E-Z isomerism aming E-Z stereoisomers n both sides of the double bond determine the priority group PRIRITY Group: The atom with the bigger A r is classed as the priority atom Priority group side 1 Priority group side 2 Z-1,2-dichloroethene E-1,2-dichloroethene If the priority atom is on the same side of the double bond it is labelled Z from the german zusammen (The Zame Zide!) If the priority atom is on the opposite side of the double bond it is labelled E from the german entgegen (The Epposite side!) ptical Isomerism ptical isomerism occurs in carbon compounds with 4 different groups of atoms attached to a carbon (called an asymmetric carbon). These four groups are arranged tetrahedrally around the carbon. A carbon atom that has four different groups attached is called a chiral (asymmetric) carbon atom This causes two 5 2 3 3 2 5 Two compounds that are optical isomers of each other are called enantiomers. This causes two different isomers that are not superimposable to be formed. They are mirror images ptical isomers have similar physical and chemical properties, but they rotate plane polarised light in different directions. ne enantiomer rotates it in one direction and the other enantiomer rotates it by the same amount in the opposite direction. A mixture containing a 50/50 mixture of the two isomers (enantiomers) is described as being a racemate or racemic mixture. Many naturally occurring molecules contain chiral atoms, but are usually found in nature as a pure enantiomer Different systems of nomenclature are is existence for optical isomers. D/L or +/- are commonly used, but both have been superseded by the more useful and informative R/S system (this is not on the syllabus for information only). ne optical isomer will rotate light clockwise (+)(called dextrorotatory). The other will rotate it anticlockwise(-)(called laevorotatory). A mixture of equal amounts of the two optical isomers will not rotate plane-polarised light. The mixture is called a racemic mixture or a racemate (-)-enantiomer (anticlockwise rotation) (+)-enantiomer (clockwise rotation) (±)-racemate (no overall effect)
hemical Reactions and ptical Isomers opyright Goalby Bancroft's School Formation of a racemate A racemate will often be formed in a reaction when a trigonal planar reactant or intermediate is approached from both sides by an attacking species : 3 : 3 3 There is an equal chance of either enantiomer forming so a racemate forms. o optical activity is seen ucleophilic addition of to aldehydes and ketones (unsymmetrical) when the trigonal planar carbonyl is approached from both sides by the attacking species: results in the formation of a racemate Mechanism for the reaction (drawn the same for both enantiomers) A racemate can also be formed in the AS reaction of the electrophilic addition of to an unsymmetrical alkene δ + δ - 2 2 3 If the alkene is unsymmetrical, addition of hydrogen bromide can lead to isomeric products. 3 + 2 : - 3 + 2 3 : - The bromide can attack this planar carbocation from both sides leading to a racemate Drug action and optical isomers Drug action may be determined by the stereochemistry of the molecule. Different optical isomers may have very different effects 3 2 3 2 2 2 3 Major product s 90% Minor product 10% 3 2 3 Thalidomide Ibuprofen 3 3 3 2 hiral carbon ne enantiomer of thalidomide causes birth defects in unborn children whilst the other had useful sedative problems. Unfortunately is was given in a racemic mixture when first used.