Daniel Christian Setioso 11 DP

TOPIC 10: ORGANIC CHEMISTRY

10.1 Introduction 10.1.1 Homologous series In chemistry, a homologous series is a series of organic compounds with a similar general formula, possessing similar chemical properties due to the presence of the same functional group, and shows a gradation in physical properties as a result of increase in molecular size and mass (see relative molecular mass). Each organic compound in a homologous series varies by an extra CH2 from the previous compound. (http://en.wikipedia.org/wiki/Homologous_series)
Homologous series is a series of organic compounds that differ from each other in the number of carbons they contain. Alkane (-ane)... only have single bonds of C-C and C-H Alkene (-ene)... has a double bond to Carbon. C=C Alcohol (-anol)... carbon has a single bond with OH. Aldehyde (-anal)... has a double bond with O and a single bond to H and an R group (occurs at end of structure). Ketone (-anone)... carbon has a double bond with oxygen and single bonds to two R groups (occurs in middle of structure). Carboxylic acid (-anoic acid)... has a double bond with O and a single bond with OH (occurs at end of structure). Characteristics of homologous series -Compounds differ by the # of CH2 -Similar chemical properties -Gradation (increasing or decreasing) in physical properties

(http://scioto.dublin.k12.oh.us/wiki/index.php/10._Organic_Chemistry) Homologous series = a series of hydrocarbon compounds that has similar chemical properties and differs only by CH2.
Carbon Atoms 1 Alkane Name Methane Chemical Formula CH 4 CH4 Structural Formula

Prefix Meth

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2 3 4 5 6 7 8 9 10

Eth Prop But Pent Hex Hept Oct Non Dec

Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Decane

C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10 H22

CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 CH3CH2CH2CH2CH3 ...

10.1.2 Trends of members of a homologous series in boiling point For example, ethane has a higher boiling point (physical properties) than methane since it has more Van der Waals forces (intermolecular forces) with neighboring molecules. This is due to the increase in the number of atoms making up the molecule. (http://en.wikipedia.org/wiki/Homologous_series) Physical properties: gradually increases Higher Mr, higher Boiling Point. Because higher Mr, stronger intermolecular forces among the molecules.

10.1.3 Empirical, molecular and structural formulas In chemistry, the empirical formula of a chemical compound is the simplest whole number ratio of atoms of each element present in a compound.[1] An empirical formula makes no reference to isomerism, structure, or absolute number of atoms. The empirical formula is used as standard for most ionic compounds, such as CaCl2, and for macromolecules, such as SiO2. The term empirical refers to the process of elemental analysis, a technique of analytical chemistry used to determine the relative amounts of each element in a chemical compound. Different compounds can have the same empirical formula. For example, formaldehyde, acid and glucose have the same empirical formula, CH2O. This is the actual chemical formula for formaldehyde, but acetic acid has double the number of atoms and glucose has six times the number of atoms. (http://en.wikipedia.org/wiki/Empirical_formula) In contrast, the molecular formula identifies the number of each type of atom in a molecule A chemical formula or molecular formula is a way of expressing information about the atoms that constitute a particular chemical compound.

Daniel Christian Setioso 11 DP The chemical formula identifies each constituent element by its chemical symbol and indicates the number of atoms of each element found in each discrete molecule of that compound. If a molecule contains more than one atom of a particular element, this quantity is indicated using a subscript after the chemical symbol (although 18th-century books often used superscripts) and also can be combined by more chemical elements. For example, methane, a small molecule consisting of one carbon atom and four hydrogen atoms, has the chemical formula CH4. The sugar molecule glucose has six carbon atoms, twelve hydrogen atoms and six oxygen atoms, so its chemical formula is C6H12O6. Chemical formulas may be used in chemical equations to describe chemical reactions. For ionic compounds and other non-molecular substances an empirical formula may be used, in which the subscripts indicate the ratio of the elements. (http://en.wikipedia.org/wiki/Molecular_formula) The structural formula of a chemical compound is a graphical representation of the molecular structure, showing how the atoms are arranged. The chemical bonding within the molecule is also shown, either explicitly or implicitly. There are several common representations used in publications. These are described below. Also several other formats are used, as in chemical databases, such asSMILES, InChI and CML. Unlike chemical formulas or chemical names, structural formulas provide a representation of the molecular structure. Chemists nearly always describe a chemical reaction or synthesis using structural formulas rather than chemical names, because the structural formulas allow the chemist to visualize the molecules and the changes that occur. Many chemical compounds exist in different isomeric forms, which have different structures but the same overall chemical formula. A structural formula indicates the arrangements of atoms in a way that a chemical formula cannot. (http://en.wikipedia.org/wiki/Structural_formula) Comparison For example, the chemical compound n-hexane has the structural formula CH3CH2CH2CH2CH2CH3, which shows that it has 6 carbon atoms arranged in a straight chain, and 14hydrogen atoms. Hexane's molecular formula is C6H14, and its empirical formula is C3H7, showing a C:H ratio of 3:7. (http://en.wikipedia.org/wiki/Empirical_formula) Structural forces: The order of repelling force from the strongest to the weakest 1. Lone pair vs lone pair 2. Lone pair vs bonded pair 3. Bonded pair vs bonded pair Note: strength of single = double = triple

Condensed structural formula: (doesn t show the bond) E.g. Pentane CH3 CH2 CH2 CH=CH2 Skeletal no H, only the bond

Daniel Christian Setioso 11 DP

10.1.4 Structural isomers as compounds with the same molecular formula but with different arrangements of atoms
Propan-1-ol (n-propyl alcohol; left) Propan-2-ol (isopropyl alcohol; right)

H H H | | | H-C-C-C-O-H | | | H H H

H H H | | | H-C-C-C-H | | | H O H | H

In structural isomers, the atoms and functional groups are joined together in different ways, as in the example of propyl alcohol above. This group includes chain isomerism whereby hydrocarbon chains have variable amounts of branching; position isomerism which deals with the position of a functional group on a chain; and functional group isomerism in which one functional group is split up into different ones. (http://www.chemistrydaily.com/chemistry/Isomerism) In structural isomerism, the atoms are arranged in a completely different order. This is easier to see with specific examples. Chain isomerism These isomers arise because of the possibility of branching in carbon chains. For example, there are two isomers of butane, C4H10. In one of them, the carbon atoms lie in a "straight chain" whereas in the other the chain is branched.

Be careful not to draw "false" isomers which are just twisted versions of the original molecule. For example, this structure is just the straight chain version of butane rotated about the central carboncarbon bond. You could easily see this with a model. This is the example we've already used at the top of this page.

Daniel Christian Setioso 11 DP Pentane, C5H12, has three chain isomers. If you think you can find any others, they are simply twisted versions of the ones below. If in doubt make some models.

Position isomerism In position isomerism, the basic carbon skeleton remains unchanged, but important groups are moved around on that skeleton. For example, there are two structural isomers with the molecular formula C3H7Br. In one of them the bromine atom is on the end of the chain, whereas in the other it's attached in the middle.

If you made a model, there is no way that you could twist one molecule to turn it into the other one. You would have to break the bromine off the end and re-attach it in the middle. At the same time, you would have to move a hydrogen from the middle to the end. Another similar example occurs in alcohols such as C4H9OH

These are the only two possibilities provided you keep to a four carbon chain, but there is no reason why you should do that. You can easily have a mixture of chain isomerism and position isomerism you aren't restricted to one or the other. So two other isomers of butanol are:

You can also get position isomers on benzene rings. Consider the molecular formula C7H7Cl. There are four different isomers you could make depending on the position of the chlorine atom. In one case it is attached to the side-group carbon atom, and then there are three other possible positions it could have around the ring - next to the CH3 group, next-but-one to the CH3 group, or opposite the CH3 group.

Daniel Christian Setioso 11 DP

Functional group isomerism In this variety of structural isomerism, the isomers contain different functional groups - that is, they belong to different families of compounds (different homologous series). For example, a molecular formula C3H6O could be either propanal (an aldehyde) or propanone (a ketone).

There are other possibilities as well for this same molecular formula - for example, you could have a carbon-carbon double bond (an alkene) and an -OH group (an alcohol) in the same molecule.

Another common example is illustrated by the molecular formula C3H6O2. Amongst the several structural isomers of this are propanoic acid (a carboxylic acid) and methyl ethanoate (an ester).

(http://www.chemguide.co.uk/basicorg/isomerism/structural.html) 1. Structural isomers (chain isomers) = compounds that have the same molecular formula, but have different arrangement of atoms (so the chemical and physical properties will be different too since arrangement of atoms affects them) 2. Positional isomers = compounds that have the same molecular formula, but the position of the bond is different. 3. Functional group isomers =

10.1.5 Structural formulas for the isomers of the non-cyclic alkanes up to C6

10.1.6 IUPAC rules for naming the isomers of the non-cyclic alkanes up to C6

Daniel Christian Setioso 11 DP

10.1.7 Structural formulas for the isomers of the straight-chain alkenes up to C6

10.1.8 IUPAC rules for naming the isomers of the straight-chain alkenes up to C6

10.1.11 Identify functional groups when present in structural formulas Amino (NH2)

Benzene ring

Esters (RCOOR)

Other resources: http://wenku.baidu.com/view/e219f5d73186bceb19e8bbdb.html

Alkane

Alkyl, and occasionally aryl (aromatic) functions are represented by the RMethyl: CH3 Ethyl: CH3CH2 Propyl: CH3CH2CH2 Isopropyl: (CH3)2CH Phenyl: C6H5 etc.

Alkyl halide

Alkyl halides [haloalkanes] consist of an alkyl group attached to a halogen: F, Cl, Br, I. Chloro, bromo and iodo alkyl halides are often susceptible to elimination and/or nucleophilic substitution reactions.

Daniel Christian Setioso 11 DP

Primary alcohol

Primary alcohols have an -OH function attached to an R-CH2- group. Primary alcohols can be oxidised to aldehydes and on to carboxylic acids. (It can be difficult to stop the oxidation at the aldehyde stage.) Primary alcohols can be shown in text as: RCH2OH

Secondary alcohol

Secondary alcohols have an -OH function attached to a R2CH- group. Secondary alcohols can be oxidised to ketones. Secondary alcohols can be shown in text as: R2CHOH

Tertiary alcohol

Tertiary alcohols have an -OH function attached to a R3C- group. Tertiary alcohols are resistant to oxidation with acidified potassium dichromate(VI), K. Tertiary alcohols can be shown in text as: R3COH

Daniel Christian Setioso 11 DP

Aldehyde

Aldehydes have a hydrogen and an alkyl (or aromatic) group attached to a carbonyl function. Aldehydes can be shown in text as: RCHO Aldehydes are easily oxidised to carboxylic acids, and they can be reduced to primary alcohols. Aldehydes can be distinguished from ketones by giving positive test results with Fehlings solution (brick red precipitate) or Tollens reagent (silver mirror). Aldehydes give red-orange precipitates with 2,4dinitrophenyl hydrazine.

Ketone

Ketones have a pair of alkyl or aromatic groups attached to a carbonyl function. Ketones can be shown in text as: RCOR Ketones can be distinguished from aldehydes by giving negative test results with Fehlings solution (brick red precipitate) or Tollens reagent (silver mirror). Ketones give red-orange precipitates with 2,4dinitrophenyl hydrazine.

Carboxylic acid

Carboxylic acids have an alkyl or aromatic groups attached to a hydroxy-carbonyl function. Carboxylic acids can be shown in text as: RCOOH Carboxylic acids are weak Bronsted acids and they liberate CO2 from carbonates and hydrogen carbonates.

Daniel Christian Setioso 11 DP

Carbonyl function

The carbonyl group is a super function because many common functional groups are based on a carbonyl, including: aldehydes, ketones, carboxylic acids, esters, amides, acyl (acid) chlorides, acid anhydrides

Ester

Esters have a pair of alkyl or aromatic groups attached to a carbonyl + linking oxygen function. Esters can be shown in text as: RCOOR or (occasionally) ROCOR. carboxylic acid + alcohol -> ester + water This is an acid catalysed equilibrium.

Amide

Primary amides (shown) have an alkyl or aromatic group attached to an amino-carbonyl function. Primary amides can be shown in text as: RCONH2 Secondary amides have an alkyl or aryl group attached to the nitrogen: RCONHR Tertiary amides have two alkyl or aryl group attached to the nitrogen: RCONR2

Daniel Christian Setioso 11 DP

Primary amine

Primary amines have an alkyl or aromatic group and two hydrogens attached to a nitrogen atom. Primary amines can be shown in text as: RNH2 Primary amines are basic functions that can be protonated to the corresponding ammonium ion. Primary amines are also nucleophilic.

Secondary amine

Secondary amines have a pair of alkyl or aromatic groups, and a hydrogen, attached to a nitrogen atom. Secondary amines can be shown in text as: R2NH Secondary amines are basic functions that can be protonated to the corresponding ammonium ion. Secondary amines are also nucleophilic.

Tertiary amine

Tertiary amines have three alkyl or aromatic groups attached to a nitrogen atom. Tertiary amines can be shown in text as: R3N Tertiary amines are basic functions that can be protonated to the corresponding ammonium ion. Tertiary amines are also nucleophilic.

Daniel Christian Setioso 11 DP

Acid chloride

Acid chlorides, or acyl chlorides, have an alkyl (or aromatic) group attached to a carbonyl function plus a labile (easily displaced) chlorine. Acid chlorides highly reactive entities are highly susceptible to attack by nucleophiles. Acid chlorides can be shown in text as: ROCl

Acid anhydride

Acid anhydrides are formed when water is removed from a carboxylic acid, hence the name. Acid anhydrides can be shown in text as: (RO)2O

Nitrile

Nitriles (or organo cyanides) have an alkyl (or aromatic) group attached to a carbon-triple-bondnitrogen function. Nitriles can be shown in text as: RCN Note that there is a nomenclature issue with nitriles/cyanides. If a compound is named as the nitrile then the nitrile carbon is counted and included, but when the compound is named as the cyanide it is not. For example: CH3CH2CN is called propane nitrile or ethyl cyanide (cyanoethane).

Daniel Christian Setioso 11 DP

Carboxylate ion or salt

Carboxylate ions are the conjugate bases of carboxylic acids, ie. the deprotonated carboxylic acid. Carboxylate ions can be shown in text as: RCOO When the counter ion is included, the salt is being shown. Salts can be shown in text as: RCOONa

Ammonium ion

Ammonium ions have a total of four alkyl and/or hydrogen functions attached to a nitrogen atom. [NH4]+ [RNH3]+ [R2NH2]+ [R3NH]+ [R4N]+ Quaternary ammonium ions are not proton donors, but the others are weak Bronsted acids (pKa about 10).

Amino acid

Amino acids, strictly alpha-amino acids, have carboxylic acid, amino function and a hydrogen attached to a the same carbon atom. There are 20 naturally occurring amino acids. All except glycine (R = H) are chiral and only the L enantiomer is found in nature. Amino acids can be shown in text as: RCH(NH2)COOH

Daniel Christian Setioso 11 DP

Alkene

Alkenes consist of a C=C double bond function. Alkenes can be shown in text as: Mono substituted: RCH=CH2 1,1-disubstituted: R2C=CH2 1,2-disubstituted: RCH=CHR Alkanes are planar as there is no rotation about the C=C bond. Alkenes are electron rich reactive centres and are susceptible to electrophilic addition.

trans-Alkene

trans-alkenes are 1,2-disubstituted functions with the two R, X or other groups on opposite sides of the C=C function. Due to the non-rotation of the C=C bond, cis and trans geometric isomers are not [thermally] Interconverted.

cis-Alkene

cis-Alkenes are 1,2-disubstituted functions with the two R, X or other groups on the same side of the C=C function. Due to the non-rotation of the C=C bond, cis and trans geometric isomers are not [thermally] Interconvertion.

Daniel Christian Setioso 11 DP

Ether

Ethers have a pair of alkyl or aromatic groups attached to a linking oxygen atom. Ethers can be shown in text as: ROR Ethers are surprisingly unreactive and are very useful as solvents for many many (but not all) classes of reaction.

Alkoxide ion

Alkoxide ions an alkyl group attached to an oxyanion. Alkoxide ions can be shown in text as: RO Sodium alkoxides, RONa, are slightly stronger bases than water and so cannot be prepared in water. Instead they are prepared by adding sodium to the dry alcohol.

Hydroxynitrile

Hydroxynitriles (also called cyanohydrins) are formed when hydrogen cyanide, H+ CN, adds across the carbonyl function of an aldehyde or ketone.

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Primary carbocation

Primary carbocations have a single alkyl function attached to a carbon centre with a formal positive charge. Carbocations - also and more correctly called carbenium ions - are important reactive intermediates implicated in electrophilic addition reactions and electrophilic aromatic substitution reactions. Stability: primary << secondary << tertiary

Secondary carbocation

Secondary carbocations have a pair of alkyl functions attached to a carbon centre with a formal positive charge. Carbocations - also and more correctly called carbenium ions - are important reactive intermediates implicated in electrophilic addition reactions and electrophilic aromatic substitution reactions. Stability: primary << secondary << tertiary

Tertiary carbocation

Tertiary carbocations have three alkyl functions attached to a carbon centre with a formal positive charge. Carbocations - also and more correctly called carbenium ions - are important reactive intermediates implicated in electrophilic addition reactions and electrophilic aromatic substitution reactions. Stability: primary << secondary << tertiary

Daniel Christian Setioso 11 DP

Acyl cation

Acyl cations have an alkyl (or aromatic) group attached to a carbonyl function with a formal positive charge. Acyl cations are important reactive intermediates and are implicated in electrophilic addition reactions and electrophilic aromatic substitution reactions. Acyl cations are commonly formed from the corresponding acyl/acid chloride plus aluminium chloride.

Polymer

Polymers consist of small monomer molecules that have reacted together so as to form a large covalently bonded structure. There are two general types of polymerisation: addition and condensation. Linear chain polymers are generally thermoplastic, while three dimensional network polymers are not.

Diol or polyol

Diols and polyols are alcohols with two or more -OH functions. Diols and polyols are very soluble in water. They are used as high temperature polar solvents.

Daniel Christian Setioso 11 DP