ࡱ> +fh;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcde'` Objbj{P{P .V::RRRRRRRtgggg<:jV *k 4n4n4n4noRaqr\ُۏۏۏۏۏۏ$ʒh2jiRyuooyuyuRR4n4nhۉۉۉyu R4nR4nُۉyuُۉۉRRۉ4nk e gw:ۉE~0ۉ ۉۉRmqr-sۉsltZqrqrqrщ qrqrqryuyuyuyuV V V 0:QV V V :QfRRRRRR Unit 5.4 Organic chemistry arenes, nitrogen compounds and synthesis 1 Arenes: benzene 5.4.1a use thermochemical, x-ray diffraction and infrared data as evidence for the structure and stability of the benzene ring Benzene structure Benzene can be represented as C6H6 or  INCLUDEPICTURE "http://www.drbateman.net/asa2topics/unit5/topic51.gif" \* MERGEFORMATINET .  INCLUDEPICTURE "http://upload.wikimedia.org/wikipedia/commons/7/7d/X-ray_diffraction_pattern_3clpro.jpg" \* MERGEFORMATINET  Evidence for the structure of benzene comes from x-ray diffraction. A pattern like the one above can be processed to indicate areas of high electron density in a molecule. See below for p-methoxybenzoic acid, which contains a benzene ring.  Task 5.4.1(a)(i).1 Draw fully displayed structural formulae for cyclohexane C6H12, cyclohexene C6H10, and benzene C6H6. Label sigma and pi bonds between carbon atoms. IR spectra indicate that benzene is different from hexane and hexene.   HYPERLINK "http://www.drbateman.net/asa2sums/sum5.3/benzenedream.htm" Story 5.4.1(a)(i)  HYPERLINK "http://www.drbateman.net/asa2sums/sum5.3/benzenedream.htm" A Dream about Benzene Benzene is more thermodynamically stable than expected if it contained 3 C-C single bonds and 3 C-C double bonds. All C-C bonds are the same.  HYPERLINK "http://www.drbateman.net/asa2sums/sum5.3/task5.3.a.i.1.htm" Task 5.4.1(a)(i).2 The enthalpy of hydrogenation of cyclohexene is given below: C6H10 +H2 --> C6H12 ; DH = - 120kJmol-1 What is the enthalpy of hydrogenation of benzene if it contains 3 C=C double bonds? The experimental value for the enthalpy of hydrogenation of benzene is given below. C6H6 +3H2 --> C6H12 ; DH = -208kJmol-1 Explain why the calculated value and the experimental values are not the same. Each pair of carbon atoms form a normal covalent bond. This leaves 1 electron left over for each C atom. These 6 electrons are delocalised across all C atoms. 5.4.1b describe the following reactions of benzene, limited to: 5.4.1b i describe combustion of benzene to form a smoky flame C6H6 + 7.5O2 ( 6CO2 + 3H2O Incomplete combustion gives carbon (soot) as product. 5.4.1b ii describe treatment of benzene with bromine Bromination: Conditions: (dry) Anhydrous AlCl3 C6H6(l) + Br2(l) ---------------> C6H5Br(l) + HBr(g) bromine bromobenzene Conditions: UV light C6H6(l) + 6Br2(l) ---------------> C6Br6(l)+ 6HBr(g) bromine 1,2,3,4,5,6-hexabromoenzene Task 5.4.1b(ii).3 Classify each reaction as an addition or substitution reaction. Task 5.4.1b(ii).4 Draw fully displayed structural formulae for each of the products. Task 5.4.1b(ii).5 Suggest safety precautions for each reactions. Task 5.4.1b(ii).6 Draw suitable apparatus for these reactions. 5.4.1b iii describe benzene reaction with concentrated nitric and sulfuric acids Benzene can be nitrated if it is boiled under reflux at 50oC with concentrated nitric and sulphuric acids (as a catalyst). This is called nitration. C6H6 (l) + HNO3 (l)---------------> C6H5NO2 (l) + H2O (l) benzene nitrobenzene 5.4.1b iv describe benzene reaction with fuming sulfuric acid Fuming sulfuric acid contains extra sulphur trioxide. This sulphonation reaction takes place at room temperature. C6H6 + SO3 ( C6H5SO3H Benzene sulphonic acid 5.4.1b v halogenoalkanes and acyl chlorides with aluminium chloride as catalyst (Friedel-Crafts reaction) Alkylation: Conditions: (dry) Anhydrous AlCl3 C6H6(l) + C2H5Cl(l) ------------------> C6H5C2H5(l) + HCl(g) chloroethane ethylbenzene Acylation: Conditions: (dry) Anhydrous AlCl3 C6H6(l) + CH3COCl (l) ----------------> C6H5COCH3(l) + HCl(g) acid chloride phenylethanone 5.4.1b vi addition reactions with hydrogen This reaction takes place at 150oC in the presence of finely divided nickel as catalyst. C6H6 + 3H2 ( C6H12 cyclohexane Task 5.4.1bvi Write equations for the reactions with hydrogen for phenol, chlorobenzene and methylbenzene. 5.4.1c describe the mechanism of the electrophilic substitution reactions of benzene in halogenation, nitration and Friedel-Crafts reactions including the formation of the electrophile 5.4.1 c Heterolytic, electrophilic substitution (benzene) Electrophilic substitution is possible in benzene rings. In this type of substitution two of the delocalised [pi] electrons on the benzene ring are donated to the electrophile. An unstable [pi] complex containing both an electrophile and a leaving group is formed as an intermediate. Nitration is carried out under reflux at 50oC using a nitrating mixture. This contains equal amounts of concentrated nitric acid and sulphuric acid. The two acids react to generate the nitryl cation NO2+ or nitronium ion. This is the electrophile. HNO3 + H2SO4 -------> H2NO3+ + HSO4- H2NO3+ -------> NO2+ + H2O HNO3 + H2SO4 -------> NO2+ + H2O + HSO4-  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.3/sum5.34.gif" \* MERGEFORMATINET   INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.3/nitro2.gif" \* MERGEFORMATINET  step 1  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.3/nitro1.gif" \* MERGEFORMATINET  -----> INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.3/nitro4.gif" \* MERGEFORMATINET  + H+ step 2  HYPERLINK "http://www.drbateman.net/asa2sums/sum5.3/electsub.htm" see animation of heterolytic, electrophilic substitution  The reaction with bromine also follows this mechanism. Aluminium chloride is used as a catalyst which helps form the electrophile.  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.3/arrow2.gif" \* MERGEFORMATINET  Br-Br + AlCl3 ---> BrD+---Br---AlCl3D-  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.3/sum5.31.gif" \* MERGEFORMATINET  Alkylation (Friedel-Crafts reaction) follows the same mechanism. Halogenoalkanes are weak electrophiles because their polar bond. e.g.CH3D+-BrD- . The catalyst AlCl3 makes the halogenoalkane a better electrophile.  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.3/arrow2.gif" \* MERGEFORMATINET  CH3-Br + AlCl3 ---> D+CH3---Br---AlCl3D-  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.3/sum5.32.gif" \* MERGEFORMATINET  Acylation also follows the same mechanism. The electrophile is again improved by AlCl3.  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.3/arrow2.gif" \* MERGEFORMATINET  CH3COCl + AlCl3 ---> CH3C+=O + Cl-AlCl3-  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.3/sumduff.gif" \* MERGEFORMATINET  Task 5.4.1c.1 Write balanced chemical equations for the mechanisms shown above. Task 5.3.1c.2 Describe a mechanism for the formation of ethylbenzene. Task 5.3.1c.3 Iron is sometimes added to bromine to catalyse the bromination of benzene. Explain how this works. 5.4.1d Practicals with electrophilic substitution 5.4.1d carry out the reactions in 5.4.1b where appropriate (using methylbenzene or methoxybenzene) 5.4.1e Reactions of phenol carry out the reaction of phenol with bromine water and dilute nitric acid and use these results to illustrate the activation of the benzene ring.G 5.4 (a) (iii) Reactions of phenol Phenol with sodium hydroxide Phenol dissolves in aqueous sodium hydroxide because phenol behaves as an acid and gives up its proton to the hydroxide ion which is a base. A soluble ionic product is formed. C6H5OH(aq) + NaOH(aq) ----> C6H5O-Na+(aq) + H2O(l) phenol sodium phenoxide Phenol is too weak an acid to react with sodium carbonate or sodium hydrogen carbonate. Phenol does dissolve to form a solution of pH just under 7. Phenol with bromine This is a substitution reaction in which an antiseptic smelling compound is formed. Note 2,4,6-trichlorophenol is called TCP. OH is electron releasing so activates the ring and speeds up the electrophilic substitution. C6H5OH(aq) + 3Br2(aq) ----> C6H2Br3OH(aq) + 3HBr(aq) 2,4,6-tribromophenol Phenol with dilute nitric acid 2,4,6-trinitrophenol is formed as a white precipitate (may appear yellow/brown) in this reaction. No conc is needed as the ring is activated by the electron releasing hydroxyl group. C6H5OH + 3HNO3 ---> C6H2(NO2)3OH + 3H2O Phenol with ethanoyl chloride This reaction forms an ester. Conditions: dry C6H5OH + CH3COCl ---> CH3COOC6H5 + HCl phenol ethanoyl chloride phenylethanoate Task 5.3(a)(iii).1 Draw fully displayed structural formulae for the products above. Task 5.3(a)(iii).2 Describe how KOH reacts with phenol. Task 5.3(a)(iii).3 Describe how 2,4,6-trichlorophenol (TCP) can be prepared. eneral nit 5 2 Organic nitrogen compounds: amines, amides, amino acids and proteins 5.4.2a amines amides and amino acids give examples of: i molecules that contain amine and amide functional groups ii amino acids All of these compounds contain an amino group but its properties are modified by its environment. amines Methylamine CH3NH2, ethylamine CH3CH2NH2, phenylamine C6H5NH2 amides Ethanamide CH3CONH2, propanamide CH3CH2CONH2 aminoacids Aminoethanoic acid (glycine) NH2CH2COOH, 2-aminopropanoic acid (alanine) CH3CH(NH2)COOH Task 5.4.2a Draw fully displayed structures for one example of each amino compound and name one more example of each. 5.4.2b Reactions of amines describe and carry out, where appropriate (using butylamine and phenylamine), reactions to investigate the typical behaviour of primary amines. This will be limited to: i characteristic smell ii miscibility with water as a result of hydrogen bonding and the alkaline nature of the resulting solution iii formation of salts iv complex ion formation with copper(II) ions v treatment with ethanoyl chloride and halogenoalkanes, eg making paracetamol smell Amines all have characteristic fishy smells. Solubility The lower amines are quite soluble forming alkaline solutions. Each amine can form hydrogen bonds with water molecules with the lone pair on the nitrogen being responsible. Phenylamine has a low solubility. Its lone pair is delocalised around the ring so hydrogen bonding is less possible. with hydrogen ions Methylamine vapour reacts with conc HCl(aq) to form white crystalline solid (smoke), methylammonium chloride, CH3 NH2 (g) + HCl(g) --------> CH3 NH3+ Cl - (s) The solubility of aromatic primary amines in increased greatly by the addition of acid. C6H5NH2(l) + H+ (aq) ---> C6H5NH3+ (aq) with copper(II) ions Solutions of amines are basic so copper ions can form hydroxide precipitates, Cu(OH)2(s). This is better written Cu(H2O)4(OH)2(s). In the presence of ammonia NH3 molecules can replace hydroxide ions and some water molecules to give a soluble complex ion [Cu(NH3)6]2+(aq). In the presence of an amine these molecules can surround copper in a complex ion e.g. [Cu(CH3NH2)6]2+(aq). with ethanoyl chloride CH3COCl + 2RNH2 ----------> CH3CONHR2 + RNH3Cl an amide making paracetomol This is a four step process: 1. Phenol is nitrated with dilute nitric acid which forms 2-nitrophenol and 4-nitrophenol. 2. Fractional distillation separates the 4-nitrophenol 3. 4-nitrophenol is reduced to 4-aminophenol with NaBH4(aq) 4. A reaction with ethanoic anhydride gives paracetomol  HYPERLINK "http://upload.wikimedia.org/wikipedia/commons/1/1d/Synthesis_of_paracetamol_from_phenol.png"  INCLUDEPICTURE "http://upload.wikimedia.org/wikipedia/commons/thumb/1/1d/Synthesis_of_paracetamol_from_phenol.png/800px-Synthesis_of_paracetamol_from_phenol.png" \* MERGEFORMATINET (  HYPERLINK "http://en.wikipedia.org/wiki/File:Synthesis_of_paracetamol_from_phenol.png" http://en.wikipedia.org/wiki/File:Synthesis_of_paracetamol_from_phenol.png) amines with halogenoalkanes halogenalkanes react with concentrated ammonia under pressure in a sealed tube to form amines. These amines undergoes further reaction with halogenalkane to make a series of new amines. CH3Cl + NH3 ( CH3NH2 +HCl CH3Cl + CH3NH2 ( (CH3)2NH + HCl CH3Cl + (CH3)2NH ( (CH3)3N + HCl CH3Cl + (CH3)3N ((CH3)4N+Cl- Task 5.4.2b How does bromoethane form amines? 5.4.2c The reduction of nitrobenzene 5.4.2c describe the reduction of aromatic nitro-compounds using tin and concentrated hydrochloric acid to form amines The acid used forms hydrogen, itself a reducing agent. 2HCl + Sn ( Sn2+ + 2Cl- + H2 C6H5NO2 + 3H2 ( C6 H5NH2 + 2H2O nitrobenzeneaminobenzene (phenylamine) Tin (II) ions are also a good reducing agent. Sn2+ ( Sn4+ +2e- C6H5NO2 + 6H+ + 6e- ( C6 H5NH2 + 2H2O 1 Heat nitrobenzene, conc. HCl and tin under reflux. 2. Cool flask and add excess aqueous NaOH. Sn(OH)4(s) + OH-(aq) ( [Sn(OH)6]2-(aq) 3. Steam distillation to give a cloudy water phenylamine distillate 4. Add saturated sodium chloride solution in separating funnel to salt out the phenyamine 5. Add ethoxyethane, shake and run off the aqueous layer 6. Add more ethoxyethane to the aqueous layer, shake and run off again 7. Repeat this solvent extraction and finally add all of the ethoxyethane fractions together. 8. Add solid potassium hydroxide as a drying agent. 9 Distill the mixture and collect the distillate between 180 and 185oC.    5.4.2d Aromatic amines with nitrous acid 5.4.2d describe and carry out, where appropriate, the reaction of aromatic amines with nitrous acid to form benzenediazonium ions followed by a coupling reaction with phenol to form a dye  HYPERLINK "http://farm3.static.flickr.com/2800/4028451478_9e552220cd_o.jpg"  INCLUDEPICTURE "http://t2.gstatic.com/images?q=tbn:pwpq3NCoul6mIM:http://farm3.static.flickr.com/2800/4028451478_9e552220cd_o.jpg" \* MERGEFORMATINET  Bright synthetic dyes Dull natural dyes HNO2 is made in situ from HCl and NaNO2 at 5oC C6H5NH2 + HNO2 + HCl --------> 2H2O + C6H5N+=N + Cl- diazonium ion Much below 5oC and the mixture may freeze. Much above this temperature and the diazonium ion decomposes to liberate nitrogen. Diazo-coupling reaction in NaOH(good solvent for phenol) at 5oC C6H5N+ = N + C6H5OH ------------> C6 H5N = NC6H4-OH + H+ a yellow azo dye (4-hydroxyphenyl)azobenzene C6H5N+ = N + C6H5NH2 ----> C6 H5N = NC6H4-NH2 + H+ an orange azo dye (4-aminophenyl)azobenzene Task 5.4.2(d).1 Draw fully displayed structural formulae for the azo dyes above. Task 5.4.2(d).2 Write an equation to show diazonium chloride reacting with C6H5N(CH3)2 5.4.2e Preparation of amides 5.4.2e recall the synthesis of amides using acyl chlorides CH3COCl + 2CH3NH2 ----------> CH3CONH CH3 + CH3NH3Cl N-methylethanamide an amide Acyl chlorides are very reactive and so room temperature is suitable. Amides are often solids so recrystallization is used in the purification process. Task 5.4.2e Write equations for the preparation of N-phenylethanamide and N-ethylpropanamide. 5.4.2f Condensation and addition polymerization 5.4.2f describe: i condensation polymerization for the formation of polyesters such as terylene and polyamides such as nylon and Kevlar ii addition polymerization including poly(propenamide) and poly(ethenol) The formation of polyesters Molecules with two carboxyl groups can join to molecules with two hydroxyl groups to form polyesters. These polyesters are important for artificial fibres. A small molecule (water, in this case) is lost for each ester bond formed. This is called condensation polymerization. nHOOCCH2(CH2)2CH2COOH + nHOCH2 (CH2)4CH2OH ------> monomer 1,6-hexanedioic acid monomer hexan-1,6-diol -(OCCH2(CH2)2CH2COOCH2 (CH2)4CH2O)n- + nH2O polymer polyhexylhexanoate ethane-1,2-diol H-O-CH2-CH2-O-H benzene- 1,4-dicarboxylic acid H-O-COC6H4-CO-O-Hpolyester terylene [-COC6H4-CO- O-CH2-CH2-O-]nTask 5.4.2f.1 Redraw the full structures of the alcohols, acids and esters above showing all bonds. The formation of polyamides  INCLUDEPICTURE "http://www.bluebird-electric.net/composites/composite_images/kevlar_bullet_proof_vest_body_armour.jpg" \* MERGEFORMATINET   INCLUDEPICTURE "http://www.jetaerospace.org/Images/kevlar_skin.jpg" \* MERGEFORMATINET  Kevlar body armour - bullet proof vest Kevlar is a polyamide used in bullet proof vests. -[COC6H4CONHC6H4NH] n - etc hexanedioic acid HOOC-(CH2)4-COOH 1,6-diaminohexane H2N-(CH2)6-NH2polyamide (nylon-6.6) (-CO-(CH2)4-CO- HN-(CH2)6-NH-)nIn the laboratory the hexane-1,6-dioyl chloride can be used to make nylon as it reacts at a quicker more convenient rate. Task 5.4.2f.2 Draw the full structural formulae for the reactants and products in the table above. Addition polymers poly(propenamide) H2C=CH -H2C-CH- | | C=O ( C=O | | n NH2 [ NH2 ]n 2-propenamide polypropenamide Cross linked chains can absorb water forming a soft substance. Polyethenol This needs a two step process. Step 1: Ethenyl ethanoate polymerises to form polyethenyl ethanoate nCH2=CHOCOCH3 ( [-CH2-CHOCOCH3- CH2-CHOCOCH3- ]n Step 2: This polymer reacts with methanol in an ester exchange reaction to form polyethenol and methyl ethanoate. [-CH2-CHOCOCH3- CH2-CHOCOCH3- ]n +nCH3OH ( [-CH2-CH(OH)- CH2-CH(OH)- ]n + nCH3COCH3 5.4.2g Structural formulae of polymers 5.4.2g draw the structural formulae of the repeat units of the polymers in 5.4.2f See 5.4.2f 5.4.2h Properties of polymers 5.4.2h comment on the physical properties of polyamides and the solubility in water of the addition polymer poly(ethenol) in terms of hydrogen bonding, eg soluble laundry bags or liquid detergent capsules (liquitabs) Nylon propertyusehigh tensile strengthropes, stockings, parachutes  HYPERLINK "http://www.google.co.uk/imgres?imgurl=http://www.hlcindustries.com/oth6.gif&imgrefurl=http://www.hlcindustries.com/aero.htm&usg=__XJAsWMm_cGopo8i9u16ZJXzsgbU=&h=256&w=250&sz=39&hl=en&start=8&um=1&itbs=1&tbnid=gxZcMW-iMdGAVM:&tbnh=111&tbnw=108&prev=/images%3Fq%3Dnylon%2Bparachute%2Bfabric%26um%3D1%26hl%3Den%26sa%3DN%26tbs%3Disch:1"  INCLUDEPICTURE "http://t0.gstatic.com/images?q=tbn:gxZcMW-iMdGAVM:http://www.hlcindustries.com/oth6.gif" \* MERGEFORMATINET low melting point INCLUDEPICTURE "http://asda.scene7.com/is/image/Asda/5051066594687?resmode=sharp&op_usm=1.1,0.5,0,0&defaultimage=default_details_George&rgn=0,0,1740,2350&scl=5.875&id=0HcTweBGSkWOGkagekjPzi" \* MERGEFORMATINET  permanent pleatinglow affinity for watereasy drying garments  INCLUDEPICTURE "http://www.beretta.com/dati/ContentManager/images/catalogo_prodotti_imgs/riduzioni/1306_big_1_340P_340P.jpg" \* MERGEFORMATINET  resistance to abrasion INCLUDEPICTURE "http://www.marwel.com/images/belt_conveyor_2.jpg" \* MERGEFORMATINET  conveyor belts, brushes, bearings in machines.Polyethenol  INCLUDEPICTURE "http://www.envirobag.co.uk/acatalog/laundrybag.jpg" \* MERGEFORMATINET  Hot and Cold Water Soluble Laundry Bags These soluble laundry bags are perfect for hospitals and nursing homes minimising the contact between staff and infected laundry. The formation of hydrogen bonds between polyethenol molecules and water enable solubility.  HYPERLINK "javascript:void(0);"  INCLUDEPICTURE "http://imagesa.ciao.com/iuk/images/products/normal/574/product-6788574.jpg" \* MERGEFORMATINET  Persil colour care tablets contain detergent in a capsule which dissolves when water enters the washing machine. The capsules are made of polyethenol which dissolves due to hydrogen bonds formed between the polymer molecules and the water molecules. 5.4.2i Amino acids 5.4.2i describe and carry out, where appropriate, experiments to investigate the characteristic behaviour of amino acids. This is limited to: i acidity and basicity and the formation of zwitterions ii separation and identification by chromatography iii effect of aqueous solutions on planepolarised monochromatic light iv formation of peptide groups in proteins by condensation polymerization v reaction with ninhydrin. See Core pract 29. Acidity and basicity An aminoacid like aminoethanoic acid (glycine) NH2CH2COOH, can act as an acid or a base. NH2CH2COOH(aq) + H+(aq) ( NH3+CH2COOH NH2CH2COOH(aq) + OH-(aq) ( NH2CH2COO-(aq) + H2O(l) In solution the acidic hydrogen of the amino acid is lost and can attach itself to the nitrogen atom in the same molecule. The result is called a zwitterion. CH3CH2 CHCOO- | NH3+ Both the zwitterion and the original amino acid structure can react with acids or bases so can act as buffers. A buffer maintains the pH of a solution when small amounts of acid or alkali are added. Task 5.4.2i.1 Draw full displayed structural formulae for the substances and ions shown above. Write equations to show how 2-aminopropanoic acid and the resulting zwitterion react with small amounts of acid and alkali. Separation and Identification  HYPERLINK "http://employees.oneonta.edu/knauerbr/chem226/226expts/226_expt11_pro.pdf" http://employees.oneonta.edu/knauerbr/chem226/226expts/226_expt11_pro.pdf Amino acids can be separated and identified by chromatography. The process needs a stationary phase (e.g. paper) and a mobile phase (e.g. suitable solvent). The sample is dissolved in the mobile phase. Different components have different solubilities and different levels of adsorption so end their journey over the stationary phase in different places. Ninhydrin is sprayed onto the dry chromatogram to show up the locations of the aminoacids. The acids take on a specific colour. Comparison with the distance moved by a standard pure aminoacid can be used to identify the acids in the sample. Effect on planepolarised light Most aminoacids have chiral centres and so exist in two optical isomers (enantiomers). An enantiomer rotates the plane of polarised light. If equal amounts of both isomers form ( a racemic mixture) rotation in both directions is equal and cancels out the observed effect. CH3CH2 *CHCOOH has a chiral centre * as the C atom shown is | NH2 surrounded by 4 different groups. (CH3CH2, H, NH2 , COOH) Task 5.4.2i.2 State which of the following would have optical isomers and why. Glycine H2NCH2COOH, L-alanine H2NCH(CH3)COOH, L-glutamic acid H2NCH(CH2CH2COOH)COOH The amino acids below link to for proteins.  HYPERLINK "http://en.wikipedia.org/wiki/File:Aa.svg"  INCLUDEPICTURE "http://upload.wikimedia.org/wikipedia/commons/thumb/3/37/Aa.svg/765px-Aa.svg.png" \* MERGEFORMATINET Task5.4.2i.3 Draw connected sequences of amino acids showing the peptide links. 5.4.3 Organic synthesis 5.4.3a importance of organic synthesis a give examples to illustrate the importance of organic synthesis in research for the production of useful products See Text Edexcel A2 Chemistry p 234-237. 5.4.3b Sensitive chemical analysis explain why sensitive methods of chemical analysis are important when planning and monitoring organic syntheses For a new synthetic molecule identify each functional group and the exact carbon chain. Choose reaction steps to build the carbon skeleton and the correct functional groups. After each step analyse (titration, IR, mass spect, NMR etc) the products to check the correct substance has been made and the yield. Alternative steps may be needed when side products are made or the yield is too low. Any toxic compounds formed must be identified and safety measures put in place. Optically active products must be made in the form of the correct enantiomer. Polarimetry is needed in analyse enantiomers. Task 5.4.3b Suppose you must make 3-phenyl-2-propenal C6H5CHCHCHO. Identify the carbon skeleton and the functional groups. If benzene and BrCHCHCOOH react in the presence of iron bromide to make an intermediate state how the mass spectrum and the NMR spectrum would change from reactants to intermediate. State how the IR spectrum of the product would change from the intermediate to the final product. 5.4.3c Empirical molecular and structural formulae C deduce the empirical formulae, molecular formulae and structural formulae from data drawn from combustion analysis, elemental percentage composition, characteristic reactions of functional groups, infrared spectra, mass spectra and nuclear magnetic resonance Starter 5.4.3c What can you say about these substances CH2, C4H8, CH3CH2CH=CH2, CH3CH=CH CH3 Empirical formula is the simplest ratio of the number of atoms of each element in a molecule of a substance. The molecular formula shows the actual number of atoms of each element in a molecule of a substance. If the empirical formula of a substance is CxHy then the molecular formula is nCxHy if n=relative molecular mass of the substance/relative molecular mass of CxHy. What is the empircal formula and the molecular formula of a compound which contains 1.2g of carbon and 0.2g of hydrogen if the relative molecular mass of the compound is 42? carbon hydrogen mass = 1.2g 0.2g amount=mass/molar mass= 1.2/12=0.1mol 0.2/1=0.2mol ratio(divide by smallest) = 1 : 2 empirical formula= CH2 molecular formula = nCH2 n = relative molecular mass of substance/relative molecular mass of CH2 n = 42/14 = 3 Molecular formula = nCH2 = 3 * CH2 = C3H6  HYPERLINK "http://www.drbateman.net/asa2sums/sum2.2/task2.2di.htm" Task 5.4.3c.1  For a compound RMM =46 1.2g C is found with 0.3g H in 2.3g of compound. The third element is oxygen. What is the empirical and molecular formula of the compound? Combustion analysis A hydrocarbon is burnt and the gases passed through conc sulphuric acid to absorb water and then through calcium hydroxide to absorb carbon dioxide. The acid increased in mass from 50.0g to 53.6g and the calcium hydroxide increased from 50.0g to 54.4g. What was the empirical formula of the hydrocarbon? Mass of water = 53.6g-50.0g = 3.60g Amount of water = mass water/molar mass water = 3.60g/18.0gmol-1 = 0.200mol Amount H in 0.20 mol H2O = 0.40mol Mass CO2 = 54.4g-50.0g = 4.4g Amount CO2 = mass CO2/molar mass CO2 =4.4g/44gmol-1 = 0.1mol Amount C in 0.1mol CO2 = 0.1mol Ratio amount C : amount H = 0.1:0.4 = 1:4 Empirical formula of hydrocarbon = CH4 Task 5.4.3c.2 0.0234g of an organic compound produced 0.0792g of carbon dioxide and 0.0162g of water. Calculate the empirical formula for this compound. (CH) Task 5.4.3c.3 Complete combustion of 0.206g of an organic compound yields 0.5666g of carbon dioxide and 0.4635g of water. Work out its empirical formula. (CH4) HW 5.4.3c From the internet collect IR, mass and NMR spectra for 2 carbon compounds e.g. ethanol and give one identifying chemical test for each. 5.4.3d use knowledge of organic chemistry contained in this specifications to solve problems such as: 5.4.3d(i) Unfamiliar compounds i predicting the properties of unfamiliar compounds containing one or more of the functional groups included in the specification, and explain these predictions  HYPERLINK "http://www.unomaha.edu/tiskochem/Chem1180/Nomenclature_Practice/Functional%20Group%20Worksheet%20Key.pdf" http://www.unomaha.edu/tiskochem/Chem1180/Nomenclature_Practice/Functional%20Group%20Worksheet%20Key.pdf  5.4.3d(ii) Planning reactions schemes ii planning reaction schemes of up to four steps, recalling familiar reactions and using unfamiliar reactions given sufficient information ethane(bromoethane(ethanol(ethanal(2-hydroxypropanonitrile 1. Br2, inert solvent, UV light 2. reflux with OH-(aq) 3. dil sulfuric acid, K2Cr2O7, distil 4. HCN in situ from KCN and HCl Task 5.4.3d(ii) Construct a network of reaction pathways and use it to construct some 2, 3 and 4 step pathways. Include:carbonyls (oxidation, reduction, addition of HCN, 2,4-DNP, Iodine in alkali) carboxylic acids (prep by hydrolysis of nitriles, reduction, neutralization, PCl5, alcohols), acyl chlorides (water, alcohols, ammonia, amines), esters (acid hydrolysis, base hydrolysis, polymerization, transesterification), benzene (combustion, bromine, conc HNO3/H2SO4, fuming H2SO4, halogenoalkanes, acyl chlorides, hydrogen) phenol (bromine water, nitric acid, formation of paracetemol) butylamine (HCl, copper (II) ions, ethanoyl chloride, halogenoalkanes), nitrobenzene with tin and HCl, aminobenzene  HYPERLINK "http://www.docbrown.info/page06/WMtestsNotes/OrgSyn01mix.htm" http://www.docbrown.info/page06/WMtestsNotes/OrgSyn01mix.htm RSC synthesis explorer  HYPERLINK "http://synthesisexplorer.rsc.org/" http://synthesisexplorer.rsc.org/ 5.4.3d(iii) Practical procedures 5.4.3diii selecting suitable practical procedures for carrying out reactions involving compounds with functional groups included in the specification An old text with diagrams  HYPERLINK "http://files.rushim.ru/books/praktikum/Mann.pdf" http://files.rushim.ru/books/praktikum/Mann.pdf Modern site with photos animation and video of A2 apparatus and techniques.  HYPERLINK "http://orgchem.colorado.edu/hndbksupport/ochemlabtech.html" http://orgchem.colorado.edu/hndbksupport/ochemlabtech.html HW 5.4.3d(iii) Draw flow diagram of apparatus for a preparation of your choice. 5.4.3d(iv) Hazards 5.4.3div identifying appropriate control measures to reduce risk during a synthesis based upon data of hazards HazardControl measureflammableNo naked flame, electric heatingNon-biodegradableNo discharge to drain, waste solvent bottleToxic-inhalationfumecupboardToxic-ingestionStandard lab ban on food and drinkToxic-skin absorbtionWear polymer glovesCorrosive Protect skin, safety glasses 5.4.3d(v) understanding why, in the synthesis of stereo-specific drugs, it is important to understand the mechanism of the reaction and how this can help to plan the synthesis Aspartame below is sweet only in the L enantiomer as this fits the sweetness receptors on the tongue. The R enantiomer is not sweet.  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