Scribd
Upload
45 views34 pages

Chemistry Unit 15

Catenation is the ability of carbon atoms to bond with one another, forming chains and complex structures, which is crucial for the vast diversity of organic compounds. Organic chemistry focuses on compounds containing carbon, with hydrocarbons being the simplest form, and functional groups significantly influencing their properties. Understanding various representations of organic molecules, such as molecular, empirical, and structural formulas, is essential for studying their behavior and reactions.

Uploaded by

khurram khan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF or read online on Scribd
45 views34 pages

Chemistry Unit 15

Catenation is the ability of carbon atoms to bond with one another, forming chains and complex structures, which is crucial for the vast diversity of organic compounds. Organic chemistry focuses on compounds containing carbon, with hydrocarbons being the simplest form, and functional groups significantly influencing their properties. Understanding various representations of organic molecules, such as molecular, empirical, and structural formulas, is essential for studying their behavior and reactions.

Uploaded by

khurram khan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF or read online on Scribd
Define catenation and its importance in organic chemistry. Recognize that hydrocarbons are the compounds of hydrogen and carbon only, Recognize that alkanes are the simplest hydrocarbons with no functional group. Functional groups determine the chemical and physical properties of organic compounds, Interpret the general, structural, displayed and skeletal formulae of organic compounds. Describe the use of systematic nomenclature of, simple aliphatic organic compounds with functional groups. 5 Peduce the molecular and empirical formulae of a compound, given its structural, displayed and skeletal formulae. Pescribe the terms saturated hydrocarbons, unsaturated hydrocarbons, homolytic fission, heterolytic {[esion, free radicals, iiition, propagation, termination, nucleophile, electrophile, Explain free radical substitution, nucleophilic addition, electrophilic addition, nucleophilic substitution, elimination and redox reactions. Describe structural isomerism and its types (chain isomerism, positional isomerism, functional groups ‘isomerism, metamerism and tautomerism. Gace ele inenegLluili ta ‘The word organic comes from Greek language “organikos” meaning organ and is generalized to organ of living organisms. The chemistry which deals with compounds having carbon is called organic chemistry. The ‘compounds which are composed of carbon Interesting Information: element are called organic compounds. On the : ‘ other hand, the compounds made of elements | carvan dioxide (COs, carbon moose other than carbon are called inorganic fHcos), cyanides (CN) and cyanates (CNO*) compounds. They come from rocks and minerals. | are inorganic compounds, though they have In organic compounds, carbon atoms are | carbon in them. The reason is that organic covalently bonded with one another and form the | compounds should have carbon directly backbone of organic compounds. In the early | bonded to hydrogen and carbon. nineteen centuries, chemists thought that organic, compounds are obtained only from plants and animals (living or once living), but not from inorganic compounds. Interesting Information ; In 1810, Jons Jacob Berzelius said that organic compounds originated from living things (plants and animals), He added that organic compounds can be synthesized only from living matter. He thought that living things have a mysterious spiritual force called vital force (vital force theory) which was needed for preparation of organic compounds. For example, urea is made inside the body of animals and cannot be synthesized from inorganic compounds in laboratory. in1828, a German chemist Friedrich Wohler, wanted to prepare ammonium cyanate (NHOCN) from the following reaction. TAGOCN yy + NH,Clag) ” > NHsOCNiaq) + ABChs) He obtained white powder from the reaction mixture which was not ammonium cyanate (NH atu CrHanesCONH | amide gM, ethanamide Acid halide ‘ CyHone1COX 1 CH,COCI R—C—cl acid halide ethanoyl chloride Arenes x Cy [Link] where "m" X= complex groups | rings group ethylbenzene Concept Assessment Exercise 15.2 Write the generat formulae and functional groups of the following homologous series i. alcohols ji, Aldehydes iii, ~—-Ketones iv. ethers v carboxylic acids vi. esters vii. amines nitriles 15.3.2 Hydrocarbons son’ and hydrogen’elements in the carbon atoms act like the backbone whereas hydrogen In hydrocarbons, atoms act like skin of molecules. Alkanes are the simplest among all organic compounds because they have no functional group, just a carbon skeleton. They are the least reactive organic compounds because of two reaso 1. the C-C and C-H bonds are very strong and difficult to be broken. 2. the C-C and C-H bonds are non-polar so cannot be attacked by other polar reagents, like acids, bases, oxidizing and reducing agents etc. Bond Bond energy (kJ/mol) Bond Bond energy (kJ/mol) CC 346 FS Ma WN 17 PP 201 0-0 142 35 26 Broadly, hydrocarbons are classified into two categories, saturated and unsaturated hydrocarbons. 15.3.3 Saturated Hydrocarbons . All alkanes and cycloalkanes include saturated hydrocarbot “saturated” is used because each carbon atom is bonded to four atoms so carbon atoms have reached their maximum combining capacity. The following are some examples of saturated hydrocarbons. H oH HOH I H ScOOH H-C—C-H L NAY tt gon HOH HegagH Hee ee HOHE Goa HH HHHH H oH H ethane butane cyclobutane cyclopentane 15.3.4 Alkyl Group (R-) Primary hydrogens are shown blue, secondary red and tertiary green. cH, He cH methane methyl CH; CH, H+ cH;CHS ethane ethyl cHycHcH, He Hed CHe Propane n-propyl (common name) CHCH>CH, H+ cH CH-CH, ropane Propel isopropyl (common name) CHyCHCHcH, = =H, GHC CHy CH n-butane (common name) n-butyl (common name) butane (systematic name) CHyCH;CHrCH, =H, GH;CHyGH-CH, n-butane (common name) secondary butyl (common name) butane (systematic name) cs qf ———1_- = CHrGH Cust CH, CH, isobutane (common name) tertiary butyl (common name) Key Information: «Primary carbon is further attached to one carbon atom or none, secondary carbon is bonded further to two carbon atoms whereas tertiary is attached further to three carbon atoms. «Primary hydrogen atoms are attached to priniary carbon, secondary to secondary carbon and tertiary to tertiary carbon atom. «In secondary alkyl, the secondary hydrogen is removed while in tertiary alkyl, the tertiary hydrogen is removed. * The prefix “iso” refers to any structure which has substituent at second last carbon of parent chain. 15.3.5 Unsaturated Hydrocarbons Since each double bonded carbon is attached to three atoms so It has the ability to bond one other atom. Similarly, a triply bonded carbon is bonded to two atoms and can bond to two more atoms. 4 -C-—c-H way y “T H-C=G-o-H H-e~ H-+C—C-H HH H 4 propene propyne cyclobutene Unsaturated hydrocarbons show addition reactions because more molecules can be added to them across the carbon atoms having multiple bonds (double and triple bonds). [Link]=Terminology Associated with’Naming| Organic Compounds For naming organic compounds, we must familiarize ourselves with some important terms. ‘Me Prefix. It may be a branch or substituent attached to the longest carbon chain. For example, alkyls and halo groups etc. The stem or root name. The stem name of organic molecules indicates the number of carbon atoms in the longest carbon chain. For example, meth, eth and prop etc. WBE. suffix of root name. There is an ending (suffix) to root name, like an, en or yn which reflects whether there is single, double or triple bond in the parent chain of molecule or not. @4e Suffix. It is the last part of an organic molecule which indicates the family name. It shows substituents . and their position on It shows saturation and the principal chain unsaturation in parent chain It indicates family name It shows number of carbon atoms in parent chain M—E—E——_——y—y———E—— $+ Class/family Prefix/Suffix Example H,CH,CH,CH, Alkanes Suffix, ane butane CH,CH=CHCH, Alkenes Suffix, ene but-2-ene CH(CH,C==CH Alkynes Suffix, yne but-t-yne CH,CH(CI)CH, Halogenoalkanes Prefix, halo Fear et ele (CH,CH(OH)CH,CH,C Alcohols Suffix, ol . el ‘ | HOCH, CH, j Ethers Prefix = alkoxy snaitonyethan’ (CH,CH,CHO Aldehydes Sufix, al propanal CH,CH,(CO)CH,CH,CH, Ketones Suffix, one pentan-2-one i ‘ CH,CH,NH; Amines Suffix, amine ethylamine a — CH,CH,CN Nitriles Suffix, nitrile propanenitrile CH,CH,COOH Carboxylic acid Suffix, oic acid propanoic acid Ei ai " CH,COCI Acid halides Suffix, oyl halide eth anoyl chloride | . CH,CONH, Amides Suffix. amide ethanamide Suffix, benzene Arenes Prefix, phenyl C,[Link], (complicated class) (varies with methylbenzene compounds) Frequently Used Root Names in IUPAC Nomenclature No of Carbon Root Name No of Carbon Root Name one ~ meth: 7 six hex two eth: seven hept- three prop- eight oct- four bute nine non- five pent= ten dec- 15.4 NOMENCLATURE OF ALIPHATIC ORGANIC COMPOUNDS Key Information: + The systematic names of all homologous series, except carboxylic acid are written as There are millions of organic compounds, many with quite one word, i a sor +The non-systematic nam complex structures, which are difficult to be named. es woe eee The International Union of Pure and Applied Chemistry some compounds in specific (IUPAC) is the universally-recognized authority on naming situations. organic and inorganic compounds. In this topic, we will 5 bring only organic compounds under consideration. It provides some internationally accepted rules to chemists for giving systematic names to organic compounds. 15.4.1 Nomenclature of Alkanes Alkanes provide the basis for nomenclature of organic compounds so we apply the IUPAC rules on alkanes first and then extend them to other families of organic compounds. Common (Trivial) Names of Alkanes: cH, Hs CH;-CH;-CH;-CH;-CH, cH;-CH-CHe CH, CH-C—CH, n-pentane isopentane H, neopentane Systematic Names of Alkanes The following rules are applied while giving systematic (IUPAC) names to alkanes, 1. Identify the longest continuous carbon chain (parent chain) i in the given compound.!The? atoms in the’ longest chain’ gives’ us root name ompou Consider the following three structures (red carbons form principal chain). CHFCHSCH-CH-CH-CH-CH, — CHGH, = GHCH, CH;-CH;-CH, GHS-GH, CHS-CH, CH, CH;-CH, In the given three molecules, there are seven carbon atoms in the parent chain so the Since there are all single covalent bonds between carbon atoms in the three molecules so they belong to alkanes family with suffix “ane”. Thus the systematic name of the given compoundsis heptane. All the three structures are straight chain molecules of heptane and identical in all respects. Key Information: 2. Identify the substituents (branches) or side |. In systematic names, a letter and chains and their position (location) and use number are separated by hyphen them as the prefixes of systematic names. In whereas the numbers are separated by commas. « Locant or locator number is the number of carbon atom on the parent chain to which a substituent is attached alkanes, alkyl groups are the substituents attached to principal chain. The position of a substituent is the number of carbon atom (locator number) in the parent chain to which it is attached, The numbering of parent chain is started from the end where substituents come closer and get the smallest locant. The substituents are shown in blue colour. CH, ‘cH oH cHe oH tHcHcH,-oH, 4-methyloctane If two identical substituents are bonded to the same carbon atom in the principal chain, repeat that locant. If identical substituents are bonded to different carbon atoms, then write their locants separately before prefixes di, tri and tetra etc. before their names. H, i bri breton om CHy“CH-CH-CH-CH—CH:CH, CH, 3,3-dimethylheptane : 3,4-dimethylheptane Hy Hy br ouesoSln ciel ~oH ot CH, 3,3,5-trimethyloctane 4. If there are two or more different substituents in a molecule, whether on same or different carbon atom in the parent chain, we write their corresponding locants separately before them and put their names in alphabetical order before the root name of the molecule, i cl Hy HH, bhecHecHbHHcHscH—cH;-cH, 5-ethyl-3-methyloctane 15.4.2 Nomenclature of cycloalkanes The following rules are used for naming cycloalkanes according to IUPAC system. nh different substituents, weiput in alpt given position one and the numbering should continue either clockwise or anti-clockwise so that the remaining substituents get lowest number at the first point of difference. CHs HyC__-CH3 CH,CHs CH 1-ethyl-2-methyleyclopropane 1,1,3-trimethylcyclohexane HC. CHy CH)CHy 2ethyl-1, 1-dimethyleyclopentane Key Information We should start numbering from the carbon where the substituent making difference comes closer, even if it violates the alphabetical order. Concept Assessment Exercise 15.3 1. Give systematic names to the following compounds. i C(CHak fi, CHsCHaCH(C:Hs)CHs iff. (CHs)sCH iv. CHy(CHa)sC(CHa)a Vv. (CHS 3C(CH2)C(CaHs)a vi. C(CzHs)s vii. = GHs Oe ‘GHs 15.4.3 Nomenclature of Alkenes and Alkynes Alkenes and alkynes follow the same rules of IUPAC nomenclature as alkanes do but they have functional group (carbon-carbon double and triple bonds) which need to be located and put in the systematic name. 1, The parent chain of alkenes and alkynes must have double and triple bonds respectively. The position of double and triple bond must follow the root name immediately which is the followed by the suffixes “ene” for alkenes and “yne” for alkynes. CH2 = CH CHs-CH = CH2 ethene propene duit, — CH CH GH EH, CH, CH, 4-methylpent-1-ene 5-methylhex-1-yne 3, If there are more than one multiple bonds in a molecule, then add “a” to the stem name and put di, tri etc before “ene” in alkenes and “yne” in alkynes. CH=C—CH=CH, CH=C—CH-CHr CH CH, CH, 2-methyl-buta-1 ,3-diene 3-methylhexa-1,5-diyne 4. For naming and putting substituents in order, the same rules are applied as for alkanes. 5. If the molecule has both double and triple bond, then we use the ending “en” for the root name and suffix “yne” for the whole molecule. 6. Numbering must be started from the end where multiple bonds come closer. If both double and triple bonds are at the same distance from either side, then prefer that side for numbering where double bond comes closer (the first alphabet “e” of “ene” comes first to the alphabet “y" of “yne”. ( CH, — but GH=cH, 4-ethylhex-1-en-5-yne HCH GH— CH CHE CH, 4-methyloct-1-en-7-yne Concept Assessment Exercise 15.4 Draw the skeletal formulae of i. but-t-ene ii, penta-1,2-diene iii, S-methylhepta-1,3-diyne iv. -_-hex-f-en-4-yne Give systematic names to the following compounds. 1. CH2=CH(CH2)3C=CCH3 ii. (CHa=CH(CH2)«CH(CHs)C=CH =CHa iv. (CHs)CH=C(CHs)CH(CHs)2 iii, CH3CH=t 15.4.4 Nomenclature of Halogenoalkanes Halogenoalkanes are those organic compounds in which one or more hydrogen atoms of alkanes are replaced by halogen atom. The halogen atom acts as functional group called halo group (X) and is treated as substituent in IUPAC nomenclature. The common names of halogenoalkanes are alkyl halides. Helogenoalkanes are named as halo substituent of an alkane. While locating the halo group, we should start numbering from that end of parent chain where halo group comes closer. We use the prefixes fluoro-, chloro-, bromo- and iodo- before the hydrocarbon part. He di a iodomethane en cHsCH- [methyliodide] anrenonde| 2-chloropropane [isopropylchloride] H, is Br CHeCH-CH;Br CHisCHrCH-cHeCH-CH, 4-bromo-2-methylpropane Cl [isobutylbromide) 2-bromo-4-chlorohexane CH, CH, onan, oH, r r CH>CHsGH-Cl i-cH-CH, CH>CH-CH;CH-CH, cl 2-bromo-2-methylpropane 2-bromo-4-methylpentane —_—_-4-chloro-2-methylhexane [tert-butylbromide] Ifa halogenoatkane has more than one halo groups, then we use di, tri and tetra ete as for alkyls in alkanes, . a, a CHrcHe Hcl Gt- CH5-G-CHyCHs-CH, 1 Br 2,4-dichlorohexane 2,2-dibromopentane 15.4.5 Nomenclature of Alcohols Alcohols make an important class of organic compounds which have hydroxyl functional group (-OH) bonded to hydrocarbon skeleton. The position of functional group is shown by the number of carbon atom in parent chain to which it is attached, The parent chain is numbered from the end where the hydroxyl group lies nearer. While naming alcohols, the “e” of alkanes is replaced by the suffix “ol”. In alcohols with more than two carbon atoms in the parent chain, the locant of hydroxyl group is written before the suffix “ol”. - CH; CH;-CH-OH CH;-GH—CH, cHee—c, ethanol OH Oy [ethyl alcohol] 1 {ethyl alcohol Propan-2-ol 2-methylpropan-2-0l [isopropyl alcohol] [tert-butyl alcohol] ‘Hy H, CH;-CH—CH;-OH CH;-C—CH;-CH-OH 2-methylpropan-1-ol du, [isobutyl alcohol] 3,3-dimethylbutan-1-ol [neohexyl alcohol} If there are more than one hydroxyl group (-OH) on the parent chain, then prefixes di, tri and tetra etc are added to the suffix “ol”. In such cases, the last alphabet “e” of alkanes is retained. The examples belong to polyhydric alcohols, having more than one hydroxyl groups (-OH). oy OH OH OH i HOH OH cert, CHy-G-CH; GH, Hi CH—CH, ethane-1,2-diol SH propane-1,2,3-triol [ethylene glycol) gemethylbutane-1,3-diol [glycerol] Alkenols have double bonds in the parent chain so the suffix “en”, | jn systematic names, two. vowels or preceded by position of double bond, is added to the root name : followed by “ol”. For numbering, the end closer to hydroxyl group | consonants giving the sound of vowels, is preferred. cannot stay together. CH=CH-OH CH=CH-CH;-OH x _ethenol prop-2-en-1-ol [vinyl alcohol] [allyl alcohol] Concept Assessment Exercise 15.5 Give systematic names to the following compounds. CH,CH(OH)CH,CH, i. (CH,),CHCH(Br)CH,CH, ii, iii, CH;CH(OH)CH(CH,)CH,CH, iv. CH,CH(CH,)CH,CH(OH)CH, vy. CH,CH=C(OH)CH, vi. CH,CH(OH)CH(Br)CH, 15.4.6 Nomenclature of Aldehydes The aldehyde group (-CHO) is always terminal so the carbon atom of this group is part of parent chain, The numbering starts from the carbon of aldehyde group always and the carbon of aldehyde group gets number 1. This is why the position of aldehyde group is not mentioned in systematic names. 9 9 9 Tl ll HOH clire-H CH}CH;-C-H CH>CH-CH>C-H methanal ethanal propanal butanal [formaldehyde] _[acetaldetiyde] _[propionaldehyde} [butyraldehyde) Numbering the parent’ chain of aldehydes is required when there are substituents attached. In common names, the carbon next to aldehyde group is alpha (a), then beta (8) and so on. cH oo a | ‘CHsSH-CH-C-H 3-methylbutanal -methylbutyraldehyde 2-ethyl-3-methylpentanal & rete) [a-ethyl-B-methylvaleraldehyde] jeanne Decal Louk CH;-CHy min 4 CH;-CH, 15.4.7 Nomenclature of Ketones The ketone group (-CO-) in ketones is always inside the parent chain so it must be a ef parent chain, While numbering the principal chain, the carbon atom of Ketone group must be alotted a number followed by the suffix “one”. Numbering should start from the end where ketone group comes nearer. The parent chains of first two members of ketones family are not numbered. All ketones are named by replacing “e” of alkanes by “one” preceded by position of Ketone group in the parent chain. 9 CH, O 9 I cl;C-cH, CH;CH;C-CH, CH;-CH-C-CH;CH, propanone butanone 2-methylpentan-3-one [acetone or dimethylketone] {ethyl methyl ketone] _[ethyl isopropyl ketone] Concept Assessment Exercise 15.6 Name the following compounds according to IUPAC nomenclature. i. HCHO fi, (CH,),CHCHO iti. — C,H;COCH, iv. CH,COCH,CH, vv. (CH,),CHCH,COCH,CH, 15.4.8 Nomenclature of Ethers Ethers have two carbon chains on both sides of an oxygen atom. While giving them systematic names, we add prefix alkoxy to alkane so they are also called alkoxyalkanes. The smaller alkyl is made alkoxy while the bigger alky is treated as alkane. CH;-O-CH, CH>-CH;-O-CH, CH;-CH;-O-CH;-CH, methoxymethane methoxyethane ethoxyethane 7 . [dimethylether] [ethylmethylether] [diethylether] 15.4.9 Nomenclature of Amines Amines are alkyl derivatives of ammonia where the hydrogen atoms are replaced by alkyl groups. If there is one alkyl bonded to nitrogen, it is primary amine. Secondary amines have two and tertiary amines have three alkyl groups attached to nitrogen atom. The systematic names of primary amines are alkanamines with “e” of alkane removed by suffix amine. CH;-NH, CH>CH-NH, CH>CH-CH-NH, methanamine ethanamine propan-1-amine [methyl amine] [ethy! amine] [n-propyl amine] NH, Ch, CHyCH-CH, cH CH-CH-NH, Propan-2-amine —_2-methylpropan-1-amine [isopropyl amine] [isobutyl amine] In secondary and tertiary amines, the alkyl groups attached to nitrogen are treated as substituents and located them just by “N”. ‘ CH>-CH-CH-N~CH;CH, N-ethy|-N-methylpropan-1-amine 15.4.10 Nomenclature of Nitriles _ The old name of this group was \C nomenclature. Nitrile compounds ” of alkanes is not cyanide but 9 are named by using suffix nitrile preceded by alkanes (the alphabet “e’ 1‘ omitted). While numbering the hydrocarbon chain, the carbon of nitrile group is counted. CH>C=N CH-CH-C=N CH;CH>CH;-C ethanenitrile propanenitrile butanenitrile [aceto nitrile] [propionitrile] Concept Assessment Exercise 15.7 1. Name the following compounds according to IUPAC nomenclature. i. CH,OCH,CH, fi. (C)Hs),CHNH, iti. (CHy)N 2. Draw 2D displayed formulae of the following compounds. N,N-dimethylethanamine i, 2-methylpentanenitrile fi. 15.4.11 Nomenclature of Carboxylic Acids The systematic names of carboxylic acids are alkanoic acids, which means that the “e” of alkane is removed by “oic acid”. The functional group of carboxylic acids is carboxyl group (-COOH) which is always terminal and its carbonyl carbon is numbered carbon 1. oO . I I H-C-OH CH;C-OH CHeCH-C-OH methanoic acid ethanoic acid propanoic acid [formic acid] [acetic acid] [propionoic acid) tl 1 CHeCH;CH-C-oH CHrCHrCHrCHrC-OH — CH-CH>CHyCHrCH;C-OH butanioc acid pentanioc acid hexanoic acid [butyric acid} [valeric acid} [caproic acid] 9 oO 9 qt wt I U il Ho-C-C-OH HO-C-CH;C-OH HO-C-CH;-CH;-C-OH ethanedioic acid propanedioic acid butanedioic acid [succinic acid] [malonic acid] [oxalic acid) g q a it HO-C-CH>CH;CHrC-OH © HO-C-CHyCH, CH; CH; C-OH hexanedioic acid pentanedioic acid nedioic [glutaric acid] [adipic acid] 15.4.12 Nomenclature of Esters The systematic names of esters consist of two parts, alkyl and carboxylate with space between them. They are derivatives of carboxylic acid. While naming, the alkyl part is written first followed by alkan “e” replaced by “oate”. oO 9 CH, O MI ae ll : H-C-OCH, CH-C-OCH, CH;CH-C-O-CH;CH, methyl methanoate methyl ethanoate —_ ethyl-2-methylpropanoate [methyl formate] {methyl acetate] [ethyl trimethylacetate] ’ 9 CH, cHC-o-GH-CH, 1-methylethyl ethanoate [isopropyl acetate] Concept Assessment Exercise 15.8 1. Give systematic names to the following compounds. i. (CH,),CH(CH,),COOH ii, (CH,COOH), iv. CH,COOCH,CH, vy. HCOOCH, 2. Draw the 2D displayed formutae of i, 2-methylpropanoic acid (COOH), vi. CH,CH(CI)CH,COOH i. oxalic acid 15.4.13 Nomenclature of Acid Chlorides Acid halides are derivatives of carboxylic acids named by removing “ic acid” of carboxylic acids with “yl halide”. 9 cHycH-cH- ec butanoyl chloride [butyryl chloride] fe) I cHecH; ci propanoyl chloride [propionyl chloride) i CH;C-CI ethanoyl chloride [acyl chloride] 15.4.14 Nomenclature of Amides Amides are derivatives of carboxylic acids. They are given systematic names by replacing “oic acid” part of carboxylic acid with suffix “amide”. In case of secondary and tertiary amides, the alkyl groups attached to nitrogen are counted as substituents by positions “N”. 9 Hee, i f fe Themes ChEU-NH, chycli; dH, CHa GN, formamide), ethanamide propanamide enaend [acetamide] [propionamide] N-methylethanamide 15.5 TERMINOLOGY OF ORGANIC CHEMICAL REACTIONS Chemical Feactions of organic compounds have complex nature so different terms are required to be discussed, 15.5.1 Types of Reagents Used in Chemical Reactions i. «Free’'Radical” his is quite unstable species so it reacts with any substance it comes across. A free radical is formed as a result of homolytic fission of molecules in different chemical reactions. Examples: chlorine radical (Ct) and methyl radical (CH), ii, (E1@¢trophile? has either positive charge or empty orbital which can easily receive electron from reaction partner (nucleophile). Example is carbocation (CHs"). ile is ar 3M or group of atoms Which is rich of electr jince it carries either a lone pair of electrons or negative charge so can easily donate electrons to a molecule (electrophile). Example is hydroxide (OH). 45.5.2 Types of Bond Breakage in Chemical Reactions during chemica Homolytic fission involves equal splitting of covalent bond between two atoms in a molecule. Each atom takes its own electron in the form of unpaired electron. This cleavage takes place because the electronegativity difference between atoms is zero or near to zero. Usually, such fission takes place between same atoms. Cl ——> 2t ii, qHeterolyticlFission)y Heterolytic fission is unequal breakage of covalent bond between atoms in organic molecules. ‘Asa result of this breakage, we get positive and negative ions. Such splitting of molecule takes place between different atoms having enough electronegativity difference. CHCl =——> CHy + Cl Po ener lkeniatiay a 15.6 TTYPES 0 ORGANIGIGHEMICAL REACTIONS. Organic compounds undergo various chemical reactions, depending upon the 1 Conditions and type of reagents used, We will study some important types of chemical according to the Prescribed syllabus. PACtion, eaCtiong In this type of reaction, a halogen free radical replaces the hydrogen atoms of al Successively and form mixture of halogenoalkanes, This reaction takes place in three Namely initiation, Propagation and termination. CH, +Cl; —™ »CH/CL+HCL kanes Steps, This type of reactions involves the attack of an electrophile (electron deficient species) on th * Multiple bond (double or triple bonds). In this way, the molecule or electrophile is added to the unsaturated compound. Alkenes show such type of reactions. In such reactions, the multiple bond is converted to single covalent bond, CH,CH= CH, +HBr ->CH,CH(Br)CH, ‘Gil Elimination Reactions)» Elimination reactions involve the removal of atoms from adjacent carbon atoms in organic ‘molecules in the form of small molecules, like H2O or HCl. Resultantly, elimination of water from alcohols and hydrogen chloride from haloalkanes gives us corresponding alkenes, CH,CH,OH—#: ¥CH, = CH, +H,0 Nucleophilic Substitution Reactions In these reactions, a nucleophile replaces an atom or group of atoms in a molecule, CH,CH,Br +NaOH -> CH,CH,OH+NaCl In this case, a nucleophile is added to molecules, usually aldehydes and ketones and the double bond between carbon and oxygen in carbonyl group is converted to single covalent bond. CH,CHO+HCN—YM" 5 [Link](CN)OH This is a chemical reaction in which a water molecule attacks the organic compound and break it into different substances. Usually, acids or alkalis act as Catalyst in this type of reactions. CH,COOCH,CH, +H,0 + »CH,COOH+CH,CH,OH Wil Condensation» Condensation reactions involve the combination of two organic molecules to form larger molecule with or without elimination of small molecules, like H:0 or HCL. Since water Is removed in this reaction so it is opposite to hydrolysis reaction. CH,COOH+CH,CH,OH—! »CH,COOCH,CH, +H,0 qitie Oxidation Reaction In oxidation reactions, organic molecules may either gain oxygen or lose hydrogen. such reactions may involve increase in number of bonds of carbon with oxygen. For example, alcohols may oxidize to corresponding aldehydes, ketones or carboxylic acids. . CH,OH+3[0] S228 >2HCOOH qixmgpmReduction Resetion® . Areduction reaction of organic molecules may involve loss of oxygen or gain of hydrogen. This type of reactions exhibit decrease in number of bonds of carbon with oxygen in the molecule. Example involves reduction of a {dehydes or ketones to corresponding alcohols. CH,CHO+2[H]—“"* »CH,CH,OH There are many organic chemical reactions, but we will study three of them with their mechanisms. 15.6, 10RreeiRadical Substitution Reaction of Alkanes In such chemical reaction, a free radical is formed first which then replaces hydrogen atoms of alkanes one after the other. It takes place with halogens in the presence of sunlight. A general substitution is shown here. 7 CHa+ Cle =——> CHCl + HCL The mechanism for this reaction is shown here. In this step, a halogen molecule splits homolytically in presence of sunlight to give free radicals. “The energy for this fission comes from the ultraviolet region of sunlight. OQ Be c+ ci This step involves the attack of halogen free radical on methane molecule to generate methyl free radical. H H LW | nda cl ——> H-¢ + Hel H methane methyl radical The methyl free radical may attack on chlorine molecule to generate chloromethang ang chlorine free radical. woe! tee +r H s+ ClCl H chloromethane If excessive chlorine is used in this reaction, then all hydrogen atoms of methane will be successively replaced by chlorine atoms to finally produce tetrachloromethane as follows, H H-¢-cl + cl —+ H-¢-4l + HCl 4 H cl cy i : H-—C—-Cl ToMe!|—» n-é-oi +*Cl 4 4 dichloromethane CI T NCY ¢ HeG—cl + Cl ——» °C—Cl + HCl H H Cl a “C—Cl + CC] ——> creel +d H H trichloromethane (chloroform) a cl : i ci—C—Cl_+ Cl ——® CI-C-CI + HCI rey . cl cl I I . CI-CG—Cl + Cl-Cl—*» Cl-C—cl + ci AND I cl tetrachloromethane ~ iii, Termination In this step, any two free radicals react with one another, at any stage, to give a neutral molecule. Termination is the death of free radicals. AN cl + ¢| — o, MY) CH; + ¢| ——» CHCl - chloromethane OW CH3 + CH; ———>CH,CH3 ethane 151612 Elimination Reactions» Elimination reactions involve removal of atoms or group of atoms in the form of molecule trom two consecutive carbon atoms. Consequently, we get unsaturated molecule (alkene) with smal molecule, mostly water and hydrogen chloride. Consider bromoethane molecule having partial positive (acidic) hydrogen and partial negative bromine atom. A base (OH? attacks acidic hydrogen making water. The bromine atom, due to its higher electronegativity, takes away the bonding electrons of carbon and leaves the molecule as bromide jon. Resultantly, elimination of hydrogen bromide takes place giving ethene molecule. fe Ve =e +f ae _ z OH + H-tCH,—CH,-+-Br ——® CH,—=CHp + H20 + Br base bromoethane ethene 56:3" Nucleophilic Substitution Reactions ~ In this type of reactions, a nucleophile attacks on the electrophilic carbon of halogenoalkane substituting the leaving group (halogen atom). bromoethane transition state [Link]"|Eléctrophilic’Addition Reactions, ‘As the name shows, such reactions involve attack of electrophile on multiple bond (pi-m bond) and converts it to single covalent bond. Here we study attack of hydrogen bromide on ethene molecule to make bromoethane. Hydrogen ion acts as electrophile in this reaction. “t toe oho — ood H nt hydrogen bromide “ethene bromoethane 15.7 ISOMERISM Organic molecules show isomerism because of the directional characters of covalent bonds. The molecules having same molecular formulae but different structural formulae are called isomers and such phenomenon is called isomerism. Isomerism is one of the reasons behind so enormous number of organic compounds. The number carbon atoms. Butane has two isomers and of isomers increases with increase in number of decane has 75 isomers. Broadly, there are two types of isomerism, structural isomerism and geometric isomerism, In this chapter, we will study structural isomerism. The structural isomers have same molecular formulae but different arrangement of atoms (structure) in molecules. It has five types. i. Chain Isomerism. Chain isomerism stems in molecules having same molecular formulae but different structural formulae with respect to length of carbon chain. CHg H3C——CH,—CH,—CH; 3 Bi 2 % H3C—CH—CH, futane 2-methylpropane ii. Positional Isomerism Positional isomers have similar molecular formulae but different position (location) of functional groups on the principal carbon chain. OH H3C-——-CH—CH; H3C—CH,—CH,—OH propan-2-ol propan-1-ol iii, Functional Group Isomerism Functional group isomerism arises in molecules having same molecular formulae but different functional groups. H,C—o—cH,—cH, HjC—CH,—CH,— 0H methoxyethane propan-1-ol iv. Metamerism Metamers have same m tength on both sides poteatar formulae but different structural formulae with respect to chain @ functional group. Metamers have same functional groups. Hy oth fh ‘CHp—CHy—CH3 HyxC—H,C —O—CH—CHy methoxypropa ¥ Tune ethoxyethane sition of hydrogen nother as a result yf isomerism which Tautomesin ‘ shown by isomers which differ with respect to different po: tom (mc le hydrogen). Tautomers exist in dynamic equilibrium with one a of intramol lecular migration of proton. Ethyl acetoacetate exhibits this type o is also called keto-enol isomerism. ° ll 1 OH t H3C—C—CH,—C—0—G,H, === Hc —C==CH—C—O— Cs keto enol Concept Assessment Exercise 15.9 1. Draw 2D displayed formulae of the possible structural isomers of i. pentane ji. propan-1-ol 2. Examine the concept of isomerism in organic compounds. © Organic compound = plants and animals. «Inorganic compounds have mineral origin. F Wohler was the first chemist who synthesized urea from an inorganic «compound (NH40CN) in laboratory and rejected vital force theory of Berzelius. Catenation means self-linking characteristic of carbon which is unique and = cannot be shown by other elements. = Displayed structural formula tells us all about bonds in a molecule but | cannot tell us about shape of molecules. This is 3D structural formula which tells us about shape of molecules also. ‘Afunctional group is an atom or group of atoms which takes part in chemical reactions. ‘Alkanes is the only family of organic compounds which have no functional group. ‘A homologous series have same functional group so it has similar chemical .e adjacent members of homologous series differ by one methylene group. to the given number 1s are found things living or once living. They came from «properties. Th ‘Ageneral formula tells us about how many hydrogen atoms can bond of carbon atoms in a molecule. Alkyl group is obtained by removal of one hydrogen atom from alkanes and has general formula CnH2n+2. Saturated hydrocarbons have all single covalent bonds among carbon atoms which include alkanes only Unsaturated hydrocarbon has at least one multiple (double or triple) bond between carbon atoms and include alkene and alkynes. Aliphatic compounds include all open chain and closed chain compounds, except aromatic compounds. ‘Aromatic compounds have at least one benzene ring in their molecules. Each IUPAC systematic name has three parts, i,¢ prefix, root name and suffix. The prefix shows substituents, root name tells number of carbon atoms in the parent chain while suffix indicates family name. Electrohphile is electron deficient species and carries positive charge. Nucleophite is electron rich species and may be negatively charged or neutral. Electrophilic addition reactions involve the conversion of multiple bonds to single bond. Nucleophilic substitution reactions involve replacement of leaving group by @ nucleophile. Structural isomerism discusses bonding of atoms in molecules, of atoms in space (structures). not about arrangement References for Further Information Organic Chemistry by T.W Graham Solomon and CB Fryhle- Organic Chemistry by R.T Morrison. Organic Chemistry by L.G Wade Jr and M Shanker Singh General Chemistry, Principles and Modern Applications by Petrucci, Herring, Madura and Bissonnette. Chemistry, The Molecular Nature of Matter and Change by Silberberg Edexcel Chemistry for A levels by George Facer. Chemistry for 1B Diploma by Christopher Talbot, Richard Harwood and Christopher Coates. Chemistry for IB Diploma by Sergey Bylikin, Gary Horner, Brian Murphy, David Tarcy. eat) 1. Choose the correct answer Which one of the following molecules needs no number in its systematic name? A. CHy(CH,),CHO B. _ CH,CH=CHCH,CH, C.— CH,CH,CH,OH D. — CH,CO(CH,),CH, 7 ve vi. Which one of the following molecules has chiral carbon? A B /\(\ On HO. Propene is converted to propane by heating with hydrogen gas in presence of nickel as catalyst. Ni(catalyst) y.¢-CHlp-CHs HyC—CH=CH, + H2 propane propene What type of chemical reaction does it belong to? A. elimination B. addition C. hydrolysis D. oxidation Sorbitol is natural compound with sweet taste and is used as substitute for sucrose by food industry. . sorbitol How many chiral carbons are present in sorbitol? A3 B.4 C5 D6 Which homologous series has highest ratio of hydrogen to carbon atoms in its general formula? A. carboxylic acid B. alcohols C. _ halogenoalkanes D. aldehydes Which one of the following hydrocarbons has no functional group? A GH, BCH CGH D. CiHyo vii. viii. How many sigma (3) bonds are present in the given molecule? CH,=CHCH,COOCH=CH, A 10 B13 C415 D 17 The systematic name of the following compound is et HsC—CH,—CH-CH-CH,—CHs cH i CH, 4-ethenyl-3-methylhexane 4-methyl-3-ethylhex-1-ene 3-ethyl-4-methylhex-t-ene A B. 4-ethyl-3-methyhex-5-ene c. D. The common name of butanedioic acid fs A. oxalic acid B, —_valeric acid C. succinic acid D. . malonic acid Which one of the following is incorrect statement about homologous series? ‘A. its adjacent members differ by one methylene (-CHz-) group B. _ its members share same functional group CC. _ its members have similar chemical properties D. __ its members have same alkyl groups Give short answer. i. Define catenation and justify that this property of carbon is responsible for so large number of organic compounds. ii. How was vital force theory rejected by Friedrich Wohler? ii, Differentiate between saturated and unsaturated hydrocarbons. Give three examples for each. iv. Define empirical formula. What are the empirical formulae of ethanol, benzene and ethanoic acid? v. Deduce the molecular and empirical formulae of the following compounds. AO vi Whatis the importance of functional group? Discuss. vii, What is alkyl group? Name and draw 2D displayed structural formulae of all - Possible alkyls: Obtained from different isomers of propane and butane. vii, Give systematic names to the following compounds. i. CH,CH,Cocl ii, CH,CN il, CHJOCH, ix, Each of the following names is wrong. Draw structures based on them and correct the names. , a. t-methylpentane b. — 2ethylbutane c. 2-methylcyclohexane d, _3,3-methyl-4-ethylheptane x. Define electrophile and nucleophile with two examples each. xi, Define chain isomerism, How can you differentiate between metamerism and positional isomerism? : xi, _ Draw and name all the structural isomers of C,[Link]., xiii, What are aliphatic compounds? Give examples. Define skeletal and 2D displayed structural formulae. Give three examples of each. Derive molecular formula of a compound with molecular mass 26 amu and empirical formula CH. What is homologous series? Write its features. What is free radical substitution reaction of alkanes? Explain bromination of methane with mechanism. . Define nucleophilic substitution and electrophilic addition reactions. Give examples of each. What is structural isomerism? Explain functional group and tautomerism with examples. Explain the difference between homolytic and heterolytic fissions of covalent bonds. How can homolytic fission initiate the halogenation reaction of alkanes? yee Create a poster illustrating common organic reaction mechanisms.

You might also like