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Organic Reactions

Alkanes with chlorine and bromine
Homolytic fission takes place � the attacking species is a free radical.

In this reaction, all curly arrows have half-heads. This denotes the transfer of a single electron. The mechanism is as follows: The initiating step is the breaking of the H-X bond by a photon of light as this bond is weaker than the C-H or C-C bonds and therefore can be broken in this way.

Alkenes undergo electrophillic addition across the double bond.

Halogens are symmetrical and add via the following mechanism:

Hydrogen Halides with unsymmetrical alkenes.

CH3CH=CH2. as the surrounding alkyl groups can release electrons to stabilise it. Concentrated sulphuric acid Alkenes react with concentrated sulphuric acid at room temperature to produce alkylhydrogensulphates. Thus the major product (about 90%) will be 2chloropropane.An unsymmetrical alkene is e. This reaction is said to be thermodynamically controlled. Thus there will be more of these carbocations available to react with the anion. Markownikoff s Rule states that when a substance of the type HX undergoes an addition reaction with an unsymmetrical C=C double bond. a =CH2 group) the H will add on to this group. RCH=CHR� + H2SO4  RCH(OSO2OH)CH2R� Note that if one of the carbon atoms across the double bond is at the end of the chain (i.e. propene. It is possible for the hydrogen to add to either the number 1 or number 2 carbon atom in the molecule. the main product is the one in which the hydrogen adds on to the carbon atom which already has the most hydrogen atoms. Since this carbocation is of lower energy (more stable). Mechanism: . The reason for this can be seen by considering the mechanism for the reaction: The secondary carbocation is more stable.g. the activation energy to form it will be lower and it will be formed more quickly.

secondary and tertiary alcohols With acidified dichromate (VI) Acidified dichromate is an orange solution. Primary. the manganate being reduced to green manganate (VI). . reforming the acid. However.2-diol is used in car antifreeze and the manufacture of terylene. Oxidation of alkenes with alkaline manganate (VII) Ethene is oxidised to ethane-1. MnO42-.Alkylhydrogensulphates are easily hydrolysed by water to form alcohols.2-diol by alkaline manganate (VII). at 300C and 60atm. Overall equation: This is Baeyer�s test for double bonds. Primary alcohol  aldehyde  carboxylic acid Secondary alcohol  ketone Tertiary alcohol � no reaction (oxidation involves breaking a C-C or C-H bond). this is a method for manufacturing alcohols industrially. ethanol is made by the direct hydration of ethene using steam and phosphoric acid as a catalyst. and acts as an oxidising agent. R(OSO2OH) + H2O  ROH + H2SO4 Since alkenes are formed by the cracking of oil. Ethane-1.

An ether is produced (in this case. In the case of ethanol. This can produce an ether or an alkene. alcohol vapour can be passed over ho aluminium oxide (acts as a catalyst). Bromination . preventing them acting as nucleophiles. ethene is formed. The mechanism is as follows: With ethanol in excess and at 140�C the ethanol molecules can act as nucleophiles and can attack the intermediate. depending on the conditions used: Concentrated H2SO4 and ethanol at 170C gives ethene. Halogenation Addition of solid PCl5 to an alcohol produces copious steamy fumes of HCl and substitutes a �chloro group for the �OH group. ethoxyethane).Achieving oxidation to the carboxylic acid requires a concentrated solution of dichromate and reflux. In the liquid state. Chlorination The alcohol is heated with concentrated HCl in the presence of anhydrous ZnCl2 catalyst. Excess sulphuric acid protonates the ethanol molecules. concentrated sulphuric acid is used. Dehydrating agents In the vapour phase.

in which case an equilibrium is set up. Carboxylic acids Esterification Acids react with alcohols to give esters and water. the amine is a "primary" amine with the functional group -NH2. Some examples of aliphatic amines:CH3NH2 methylamine C2H5NH2 ethylamine C4H9NH2 butylamine etc An aromatic amine C6H5NH2 phenylamine The amines. As esters have no hydrogen bonds. This is a messy reaction as Br2 is also produced. Where just one hydrogen is replaced. or alkali. Iodination A mixture of red phosphorus and iodine acts like phosphorus (III) iodide. The substitution proceeds as above. This reaction is catalysed by H+ ions. One other product is phosphonic acid. which allow the nitrogen to accept a proton more easily. they are more volatile than the other reagents and thus can be removed by distillation during the process.g. like ammonia. This can then by converted back to the acid using a mineral acid (e. They are actually slightly stronger bases than ammonia because the alkyl groups release electrons. pushing the equilibrium to the right. Esters are hydrolysed using either acid as a catalyst. This then carries out the iodination. in which case the salt of the acid is produced. 3ROH + PI3  3RI + H3PO3 Primary amines with hydrogen ions An amine can be viewed as an ammonia molecule in which an alkyl or aryl group has been substituted for a hydrogen atom. H2SO4). .The HBr required is produced in situ by the reaction of concentrated sulphuric acid with KBr. act as bases and accept H+ ions. This mixture is then heated with the alcohol. usually in the form of concentrated sulphuric acid as this removes water.

The once commonly used is lithium tetrahydridoaluminate(III). and HCl and an acyl chloride is produced. referring to an (organic) compound containing a benzene ring. HNO3 + 2H2SO4  NO2+ + H3O+ + 2HSO4For activated arenes (e. The reaction between the two produces the NO2+ ion. dilute nitric acid and sodium nitrate is used.Reduction A powerful reducing agent is needed to reduce an acid.g. toluene). This mixture is refluxed with the benzene at 60�C. The solvent usually used is dry ethoxyethane. Mechanism: Oxidation of side chains with manganate (VII) . It needs to be used in completely anhydrous conditions or hydrolysis of the agent takes place. phenol. The first step of the mechanism is shown below. To nitrate benzene a mixture of concentrated nitric and sulphuric acids is needed. which attacks the electrons on the benzene ring. or ether. giving an electrophillic substitution. Phosphorus pentachloride When solid PCl5 is added to a carboxylic acid at room temperature a vigorous reaction occurs. or litium aluminium hydride. Arenes Arenes with nitrating mixture The term "arene" is equivalent to the term "aromatic".

although not so in synthesis. It is carried out using a chloroalkane in the presence of anhydrous aluminium chloride as a catalyst. This is very useful in diagnosis. The mechanism is as follows: The chloroalkane reacts with the AlCl3 to form an electrophile: This then substitutes into the benzene ring. will oxidise all side chains on a benzene ring to carboxylic acid groups. dilute. Halogenoalkanes Hydroxide ions With a cold. the same reaction takes place. aqueous solution of hydroxide ions nucleophillic substitution takes place by the SN1 or SN2 mechanism.Hot concentrated manganate (VII). RCH=CHR� + H2O +X- . acidic or neutral. SN1 takes place mainly with tertiary halogenoalkanes (see module 2 notes). Friedel-Crafts The Friedel-Crafts reaction is a method of introducing a side chain onto a benzene ring. but leading to the first group on the chain being a carbonyl group. which may be useful for reactions. alkaline. This is useful because it allows compounds to be synthesised from the benzene. reforming the catalyst. If an acid chloride is used in the place of the chloroalkane. RX + OH. RCH2CHXR� + OH. ROH + XWith a hot concentrated ethanolic solution of hydroxide ions elimination of HX takes place to give an alkene.

It is necessary to use the organic solvent as water reacts with the cyanide ions to form HCN and OH ions. It is essential for the conditions to be anhydrous. the reaction is not as clear-cut as this. The more extreme the conditions the greater the yield of the required product will be. Cyanide ions With cyanide ions in ethanolic solution. which then substitute instead. RX + Mg  R Mg X The distribution of the charge on the atoms should be noted: . not least that the primary amine produced is a stronger base than the ammonia itself. nucleoplillic substitution takes place. With ammonia With ammonia nucleophillic substitution takes place. The equation is RX + NH3  RNH2 + HX This process has many problems. it can be reacted with magnesium to produce a Grignard reagent. This is avoided by using a great excess of ammonia. Ammonia gas must be used under pressure and heated in a sealed container. and therefore will react with the halogenoalkane itself. otherwise the Grignard reagents will react with the water. Grignard reagents If a halogenoalkane is dissolved in dry ethoxyethane.Obviously. The mechanism is as follows: If the halogenoalkane was optically active then the resulting compound will also be optically active. This is necessary also because the HX produced will react with ammonia. Some substitution takes place in the ethanolic solution and some elimination in the aqueous case. If the CN increases the chain length then the compound is named as a nitrile. If not it is named as a compound with a cyano group substituted. but causes problems with the removal of the excess ammonia afterwards.

which is virtually useless. in which case a carboxylic acid is formed. This is easier than trying to substitute ammonia into the benzene ring. this route is too expensive. and a magnesium salt. but the suspension produced is difficult to handle. The reaction with water is: R-Mg-X + H2O  RH + Mg(OH)X As can be seen. The mechanism is basically the same: In both cases. which could be useful to produce carboxylic acids that are not found in nature. It can then be converted to phenylamine by reduction. which can act as an electrophile. The hydrolysis could be carried out by water alone. In the lab. this uses up the reagent to form an alkane. a very unusual species in organic chemistry. the reaction is accomplished using tin metal and concentrated hydrochloric acid. Reduction of nitrobenzene Nitrobenzene is easily produced by the nitration of benzene. This produces a carboxylic acid with an extra carbon atom. In industry. Reacting this complex with an aldehyde or a ketone gives a secondary or tertiary alcohol respectively. The reaction mechanism for a general carbonyl compound is shown: The reaction is also possible with carbon dioxide. The reaction with tin is: . and iron is used with the most dilute hydrochloric acid that will carry out the reduction. MgXCl is also produced.This is a carboanion.

and therefore no coloured precipitate is formed. resulting in highly coloured compounds used as dyes and acid base indicators. Possibilities are aromatic amines and alcohols. This gives the reaction NaNO2 + HCl  NaCl + HNO2. This links the two aromatic groups with an N=N group. It reacts with phenylamine in the presence of excess acid to produce benzene diazonium chloride: It is necessary to keep this reaction cold � below 5�C � otherwise the diazonium salt decomposes to give nitrogen gas and a poor yield of phenol. with nitrous acid. also known as nitric(III) acid. This is produced by dissolving sodium nitrate (III) (sodium nitrite) in dilute hydrochloric acid. benzene diazonium chloride with phenol and 2-napthol: The reaction with 2-napthol can be used to distinguish between aliphatic and aromatic amines. With aliphatic amines.The reaction with iron is very similar. is called diazotisation. except that iron(III) oxide is formed instead of tin(IV) chloride. Carbonyl compounds . The production of azo dyes Diazonium compounds are produced by reacting aromatic amines. Coupling Coupling is the reaction of a diazonium salt with an activated aromatic compound. This is achieved by adding ice to the reaction mixture. For example. as it produces diazonium salts. particularly phenylamine. This is pale blue in colour and not very stable. where HNO2 is nitrous acid. This reaction. stable diazonium ions do not form.

but not with a ketone. The mechanism for the reaction is: As shown. The reaction adds a carbon atom to the chain. 2. as a ketone cannot be oxidised. The reaction is inhibited by acids. Tollens� Reagent (ammonacial silver nitrate solution) Tollens� reagent contains Ag+ ions.4-dinitrophenylhydrazine (Brady�s reagent) This is addition followed by elimination. This is a nucleophillic addition reaction. an aqueous solution of potassium or sodium cyanide is used. It can thus be used to distinguish between an aldehyde and a ketone. This reaction is possible with an alcohol or an aldehyde. which can be reduced to silver metal. This is the substance that is analysed. With a positive test (aldehyde) a silver mirror forms on the inside of the test tube used. the initial product rapidly looses water to form a hydrazone.Hydrogen cyanide To provide this addition. but the overall reaction is the addition of HCN. which can be recrystalised and the melting point determined to give a precise diagnosis of which carbonyl was present. and also allows acid hydrolysis to -hydroxycarboxylic acids. the mechanism is as follows: The compound produced is usually referred to as the cyanohydrin of the carbonyl compound � it can also be named systematically. The product formed is a yellow precipitate. also called a condensation reaction. giving a qualitative diagnosis of a carbonyl compound. .

or acyl chlorides. it is easier to use because it can be used in aqueous solution. However. . allowing nucleophillic attack and fission of the bond: The products are iodoform and a degraded carboxylic acid. It reduces aldehydes to primary alcohols and ketones to secondary alcohols. and thus they react vigorously at room temperature. This causes a great withdrawing of electrons from the C-C bond joining the methyl group to the ketone group. The reaction starts with the substitution of the hydrogens in the methyl group for iodine atoms. The presence of the �Cl group makes them more susceptible to nucleophillic attack than the corresponding carboxylic acids.The iodoform test The iodoform test is a test for compounds that contain either of the following groups: This includes ethanal and ethanol. Ethanoyl chloride � CH3COCl Acid chlorides. A bright yellow precipitate of iodoform indicates a positive test. and is cheaper. Sodium tetrahydridoborate (III) � sodium borohydride � NaBH4 This is a milder reducing agent than LiAlH4. fume in air (HCl). This reaction is of more value for diagnostic purposes than for synthesis. Ethanoyl chloride can be manufactured by treating ethanoic acid with phosphorus pentachloride. If a methyl secondary alcohol is used it will be oxidised to the methyl ketone before the main part of the process takes place. The compound being tested is reacted with iodine in sodium hydroxide solution or sodium chlorate (I) and potassium iodate solution. and will not reduce carboxylic acids and their derivatives.

Ethylamine CH3COCl + C2H5NH2  CH3CONHC2H5 + HCl Phenylamine: Nitriles . and therefore acid chlorides must be used in anhydrous conditions. CH3COCl + H2O  CH3COOH + HCl Ethanol Esterification takes place. CH3COCl + 2NH3  CH3CONH2 + NH4Cl Primary amines The reaction with primary amines is basically the same. CH3COCl + CH3CH2OH  CH3COOCH2CH3 + HCl Ammonia Again. although this is not shown.Water The acid is reformed with the production of hydrochloric acid. at a faster rate than with the acid and alcohol mixture. except that a secondary amide is produced. the ammonia substitutes for the chloride group to produce a primary amide. Again. the HCl will react with excess amine. This is a vigorous reaction. The HCl eliminated then reacts with excess ammonia.

a nitrile.Nitriles are organic compounds where the chain is terminated by a CN group. the ammonium salt of the mineral acid and the carboxylic acid. lithium aluminium hydride Hydrolysis of nitriles is carried out by refluxing with acid or akali. leading to a compound with one less carbon atom. Dehydration is carried out by heating with phosphorus(V) oxide (P4O10).g. Amides Amides can be used in synthesis to add the amino group onto a molecule. This gives the following reaction: The product. This can be done via a degradation (the Hofmann degradation).water hating Lipophilc .g. If alkaline hydrolysis is carried out then ammonia is produced and the sodium salt of the acid formed. for example. CH3 CH2CN. The ammonium salt is not actually produced. Other reduction mechanisms are possible. Reduction of nitriles is with hydrogen in the presence of a nickel catalyst. propannitrile. or via dehydration to give an amine with the same number of carbon atoms. .water loving Hydrophobic . can be reduced (e. e. RCN  RCONH2  RCO2-NH4+ In practice. This proceeds through an amide to the ammonium salt of the acid. Hydrophilic . but in the case of acid hydrolysis. with hydrogen and a nickel catalyst) to give an amine. The naming of the nitrile includes the carbon that the nitrogen is bonded to. stopping at the amide is not easy. The Hoffman degradation is carried out using bromine and aqueous alkali: RCONH2 + Br2 + 2NaOH  RNH2 + CO2 + 2NaBr Targeting Pharmaceuticals This is to do with a balance between solubility in water / watery tissue and solubility in fat / fatty tissue.fat loving To adjust the behaviour of a substance we adjust the functional groups attached. This gives a primary amine.

-CONH These groups can hydrogen bond with water. Lipophilic / hydrophobic functional groups Alkyl groups and benzene rings . Oil of wintergreen is insoluble and is applied to the skin to relieve the pain of arthritis. . Concentration in the bloodstream remains too low. -NH2. which are excreted via the urine. Both aspirin and oil of wintergreen have analgesic properties. 2. To make it more soluble and therefore easier to take the sodium salt can be prepared .hydrocarbon groups Solubility and retention time If the substance is too lipophilic (insoluble): 1. If the substance is too hydrophilic (soluble): Retention time is too low .Hydrophilic functional groups -OH.this converts back into the usual form in the acidic conditions in the stomach. It may not be sufficiently absorbed. -CO2H. -NH. Aspirin is very soluble and dissolves easily in the bloodstream.the substance is quickly transported to the liver and broken down into soluble products. but the different groups attached to the benzene group give them different solubility properties.

Its original form. An even more soluble derivative. penicillamine. can be formed. . Heating methods: 1.Penicillin is an important drug that acts by preventing bacteria forming cell walls and thus reproducing. was very soluble and rapidly excreted . Organic Preparations Step 1 . using 2 molecules to surround a metal ion. Direct heating with a bunsan burner This is relatively rarely used in organic preparations as organic chemicals tend to be highly flammable and the heat produced is not smooth.Getting a reaction to occur      Unless other information is is also helpful to remove the product(s) as they are produced.the other reagents should be in excess. If the reaction is an equilibrium then an excess of one reagent should be considered . penicillin G. assume a 60% yield at this stage.lipophilic side chains are added to make it less soluble. Co-ordination takes place with the marked lone pairs. which complexes with heavy metals and is then excreted very rapidly. removing the poisonous metals from the body. The most expensive reagent should be used as the limiting factor . Heating under reflux gives the highest possible temperature for that mixture in the liquid phase (the boiling point) without loss of product or reagent.

If the boiling point is above 180�C then an air condenser is used. The solvent should be chosen so that the substance is as soluble as possible at high temperatures and as insoluble as possible at low temperatures. Distillation under reduced pressure is used if the product is likely to decompose at its usual boiling point. 3. Different oils are used for different temperatures. Insoluble impurities are removed by hot filtration (running a little hot solvent through the funnel first or heating the funnel during filtration) or fast filtration (using a fluted filter paper and a funnel with a broken arm). a pure product cannot be obtained. The filtration apparatus is then reconnected and the product dried. and then separates out in the cooled water. .2. 2. The solvent is added and the product dissolved. the larger a column needs to be used. 3. Waterbath This is used for low temperatures (<100�C). It may be necessary to induce crystallisation by the use of ice or scratching the side of the beaker with a glass rod.Purification  Solids are purified by recrystallisation 1. The solid is dissolved in the minimum quantity of hot solvent (minimum quantity to increase yield).Separating       Simple distillation can be used if the boiling point is less than 250�C and no other volatile product or reagent is present. Fractional distillation is used for mixtures of liquids. Allow the solution to cool to recrystallise the product. Step 2 . 4. the liquid is separated off by filtration and the product separated from the solvent by fractional distillation. Ethoxyethane is often used. dries the product as well as filtering it and allows the product to be washed easily. It is more efficient to use the solvent in several smaller portions (usually 3) than all together in one portion. Oilbath This is used for higher temperatures (<300�C). The product dissolves in the steam and distils over with it. Steam distillation can be used for a product that has a high boiling point and is insoluble in water. Solvent extraction is used where there is a solvent that the product dissolves in but the impurities and remaining reagents do not. Buchner filtration is used as it is faster. Step 3 . The solids produced are filtered with a Buchner funnel and washed with a little cold solvent. If the boiling points are too close. Too low a temperature should not be used or the impurities will recrystallise as well. The closer the boiling points are. otherwise a Leibig water-cooled condenser.

3. Release the pressure regularly when shaking with a substance. calcium oxide (often used with alcohols) and sodium sulphate. acid impurities with sodium carbonate and ethanol with calcium chloride. Dry the liquid by standing it on anhydrous drying agent (may take up to 48 hours). Soluble impurities should be removed with water. 2. collecting the fraction that distils within 1�C of the boiling point of the liquid . Drying agents commonly used are calcium chloride (not with alcohols). Distillation completes the process. Liquids are purified as follows: 1. Wash to remove impurities using a separating funnel.