Chapter 3 ALIPHATIC HYDROCARBONS Compounds containing carbon and hydrogen only in their molecules are called hydrocarbons. They mostly exist in natural gas and petroleum. On the basis of structure these are divided into two main classes, aliphatic and aromatic hydrocarbon. Aliphatic hydrocarbons are further divided into four families, ‘e,, alkanes, cycloalkanes, alkenes and alkynes. ALKANES AND CYCLOAKANES ALKANES : Alkanes, also known as paraffins, have the general formula CyHpq42: Since the valency of carbon atoms, in their formulas, is completely satisfied, alkanes are known as | saturated hydrocarbons. By increasing ‘n’ gradually we obtain the formulas of a series of compounds in which every member differs from its immediate, neighbour by one~CH | group. Such a series is known as a Homologous series. ’ ‘The first four members of this series are gases with the following structures. | H H H HOH H H HH I aa el fi, dee le of E | | | H H.H H HH bida methane ethane propane butane Methane, CHy, the first and the simplest hydrocarbon, is a principal constituent of Natural Gas which is widely used as fuel. The next higher homologues, ie., pentane, hexane, heptane, octane, nonane and decane are liquids and the still higher members are waxy solids. | Nomenclature There are two types of names for alkanes, trivial oe ; or common names and IUPAC } Trivial or Common Names: The trivial nomenclature i is not systematic, because | = compounds were hamed long before their structures were eae For example name marsh gas was given to methane because it was found in marshy places, and (87)38 Organic Chemisty - butyric acid. The hi derived from a related compound Righer the name butane was based on Greek numbers, i.e., penta for five, hexa for six homologues have nomenclature - and soon. s : structures of first four alkanes, i.e., methane, ethane, propane ang, ee of 4) and hydrogen (valency of 1), we find that while cucme wn ee fer homologues have only one possible structure, the formula of propane 206 {BS sspords to two possible structures which can be written as follows. butane-C.Hyy H oH Bau yo aed a_é_t- tH and H-C—f—C-H © as HAC H isobutane straight chain and iso indicating branched-chain is used (Two different compounds are said to be isomers if they have the same maiecular formula). There are three isomers of pentane, i.e., n-pentane, isopentane and neopentane. ie CH—CH,-CH,-CH,—CH, as CH,CH; Sari CH CH; CH; n-pentane isopentane neopentane The . Ba Rew prefix neo stands for a compound having three methyl groups at one The number of isomers for higher alkanes i enormous! are5 increase Thus there Somes: for hexane, 18 for octane and as many as 73 for decane, Tae ° = ee an any name becomes difficult. A more systematic =o pee ws therefore opted by the jnfemational Union of Pure and Applied Problems, and is known as the IUPAC nomenclature,” iiedeslingt ori. 5 subvanzent on another portion, the subst emer. Of AYdrocarbon is i . general name of the comp ‘sana referred to as considered as To obtam the name of the ; alkyl Thus CH;— is methy! i “Y! group, the ~an ’ es PNM oained from CHy methane py Placed ith 3 ” °Y replacing ~ane with -¥Po ee Aliphatic Hydrocarbons 99 The names and short symbols for some of the common alkyl groups are given in Table 3.1 . “ TABLE3.1 Alkyl Group Name Short Symbol CH;— Methyl Me CH3— CH) — Ethyl Et CH3— CH, —CH,— n-Propyl n-Pr CH3—CH— M Isopropyl i-Pr CH, CH3— CH) — CH, — CH) — n-Butyl n-Bu CH3—CH—CH) — aa : Isobutyl _ BBu CH; CH3—CH,—CH— . | sec—Butyl s-Bu CH; oH ea tert-butyl t-Bu CH The names sec-butyl and tert-butyl indicate that in these alkyl groups the points Of attachment are at the carbon’ atom connected respectively, to two and three other carbon atoms. voting eM fF naming hydrocarbons by IUPAC system may be summarized as follows: 1. Find the longest continuous chain of carbon atoms, and use the name of this long chain hydrocarbon as the base name of the compound. _ For example, the longest chain of carbon atoms in the following compound Contains six carbons. The compound is therefore named as some derivative of hexane. CHy—CH CH;—~CH —CH,—CH,—CH, Member the longest chain beginning with the end of the chain nearest a substituent. In the ‘© example numbering from one end places substituent at number 3, while from the00 © Organio Chemlatry i 1 wing, Which gives @ sali othor end the substituent falls at number 4: The numbering, ile number to the substituent Is correc ti 2 1 CHy-CHy 2 é 1, CH CH, CHy = CH CH = Ga f tached to the longest chain, and give the 3, Name each of the alkyl oubstituent group 4) lM focation of each alkyl group by the number of the carbon atom of the main chain to which it ig attached, ‘The name of the substituent (given and it is present at the carbon atom of the the compound in the above example In named a systematic or the IUPAC name of the compound, 4, When two or more substituents are present, st them in alphabetic order, and when two or more of the same alkyl substituents are present, use the prefixes di-, tri-, tetra, and 60 on, ‘The IUPAC name of the following structure, in Table 3,1), in the above example is methy| chain which carries the number 3, Therefore 6 3~methylhexane. This name is called CHy CH, cH —eH —Chh— —CH, CH, is, therefore, 2,2A-trimethylpentane as the lon ngest chain ic ine methy! substituents are attached at cavbon numbers 2 2 oon, petit but the two methyl groups are attached to carbon number 2.” Here 2,2-means that If there are two or di ; placed in alphabetic order, ‘more diferent kinds of alkyl Sroups present, their names are The following structures, ther i theref cn ; fore, have the IUPAC names given below each. i CH, CHy~C—CHy~CHy ~CH—CH, —CH, CH, — é én ~CH,—c| SZ H, bit,-ci, by . ! ak 5 CH —CH, S-ethyl-2,2, dimethylheptane 5 tr octane Notice that ¢ - di ee ln abet na Used j in alphabetizing, alphabetic order, the prefixes tert; s¢- Methods of Preparation of Alkanes Alkang Methane, es occur in fraction of Nature in ty ethane, Propane a remendous 7 Ine and by quantit Petroleum distillation, Hanes are isa ties in Petro} r 1s TOM natural gas and the lightAliphatic Hydrocarbons 94 In the laboratory alkanes may, however, be prepared starting from othe m other classes of organic compounds. 1. From unsaturated hydrocarbons. When a mixture of hy . drogen gas unsaturated hydrocarbon (alkene or alkyne) is passed over finely divided planar aon catalyst, at room temperature, the unsaturated hydrocarbon is converted to an creel i Pt j CH,=CH) +H, —> _CH3—CH3 ethene ethane ( cH acH+ay—. a—cHy acetylene : This process is known as catalytic hydrogenation and is important as certain unsaturated hydrocarbons, such as, ethylene and acetylene, are readily available starting materials. 2, From alkyl halides. Alkyl halides may be converted to alkanes by different reagents. > (i) By simple reduction of Alkyl halides. Alkyl halides are reduced to alkanes with any one of the reducing agents such as Zn + Alcohol, Sn + HCl, or LiAl Hy. CH,—CH, Br“, cH, cH, (ii) Wurtz reaction. When ethyl bromide, in ethereal solution, is treated with metallic sodium, n-butane is obtained. Na ' 2CH,—CH,—Br ——* 5 CH, CH, CH, —CH, + 2NaBr * n-butane Similarly methyl iodide gives ethane. In this way it is possible to get CeoHiz2 from CagHiCl by the action of sodium. reaction 2, hat whereas simple reduction of ethyl bromide gives ethane, Wurtz ae of ethyl bromide gives n- butane. So Wurtz reaction may be used to build up A mixture of Alkyl halides, however, gives a mixture of alkanes. For example, a mixture of CH! and CH;CHyI gives ethane, propane and n- butane as shown in the following equations. CHJ+ CHIN, cHycH, oN CHyl + G)Hsl "5 CH,—CH,—CH, Na GHsl + CHs| ——4 C)Hs—CHsAliphatic Hydrocarbons 95 Reactions of Alkanes The alkanes specially the straight chain alkanes are resistant to attack by powerful reagents such a concentrated sulphuric acid, nitric acid, fused alkalis, potassium dichromate or permanganate. Due.to this lack of reactivity, the hydrocarbons of this series are referred to as paraffins (Latin, parum, ‘little’, and affinis, ‘affinity’. They, however, undergo substitution reactions, in which a hydrogen atom of the alkane is replaced by some other atom or group, if conditions like temperature, and pressure are made sufficiently severe and some catalyst is also involved. Some important substitution reactions of alkanes like halogenation, sulphonation and nitration alongwith some reactions like oxidation and pyrolysis are discussed below. a. Halogenation: A substituation reaction in which hydrogen atom of an alkane is replaced by a halogen atom (F, Cl, Br, or 1), is called halogenation. It takes place under the influence of heat or light. Thus chlorine reacts with methane in the presence of sunlight to produce HCl and methylchloride (CH,C)). h CH,+Ch—" cH, Cl+ HCI As the concentration of CH,C! builds up it can itself undergo further substitution to form HCl and methylene chloride (CH,Cl,) : . ; CHC1+ cl — 5 crcy +HCI _ in a similar way chlorination can continue to yield chloroform (CHCl,) and carbon tetrachloride (CCl), hv CH,Cl, + Ch ——> CHCL, + HCI h CHCl + cl —" scc1, + HI nea of methane is a photochemical chain reaction involving free radical a m nea that large amounts of products are formed after the chlorine, na SOrbs light to produce a small amount of free radical chlorine. The com lete mechanism involves the following three steps, : Step I - Initiation . : : Ns ae aie cilorine free radicals are formed. This happens when the = ar of igh is ab ¥ chlorine molecule and cleaves CI—Cl bond to give two hv . cl, —— > 21ee AN Aeagnte Rho ont 06 © Organio Chemiatry ftep Propagation first one free radical chlorine is Phere are two propagation steps In the conmumed and a nev free radical CH io formed. This happens when Cf attacks CH, and abetracts a hydrogen forming, HCV CHy+ Cl ——— CH, + HC In the second propagation step My attacks Cl, forming CHCl and regenerating Cy + ly CHI 4Ch Thus in the two propagation steps the free radical Cf is being consumed and regenerated again and again until the chain reaction terminates. Step It ‘Termination: In the termination step the fre radicals are annihilated and thus the propagation of the chain reaction stops, CH +f ——+ CHI CH) + CHy-——+ CH,CH, cf +cf —+ch, ah The Gilorination of methane does not stop at the formation of mono chloro os ne but continues, as mentioned above, and gives rise to a mixture of di, tri and ine chloro methanes from which CH,CI can be obtained by fractional distillation. urination of methane in, therefore i a tesa , ¢, not a useful laboratory reaction for the preparation pebile ipsa ‘The quantity of methyl chloride can however be increased by using ‘The seine ale ani iene 6 8-1 Te nine i attack of either Br’ or I on methane in the first tion nol enerystically favourable as compared to, the attack of F” or Chon CH, as os below. . rir rcHs AH = -138 kj mol Wy Coe +H, AH = 5k mol? ph ie Cs AH = +63 mor! PH OH, +H, AH = +190 kf mol?Allphatic Hydrocarbons 99 (isooctane) with octane number of 100. The octane number Of a fuel is, therefore, an arbitrary ratio of ‘sooctane and n-heptane. Branched chain alkanes and alkenes have excellent antiknock qualities. These materials are Produced from petroleum hydrocarbon by processes known as Catalytic cracking and catalytic reforming. Octane number of a fuel may also be greatly improved by addition of a small amount of (CH,),Pb. One of the public concems, in general, is to clean up the poisonous exhaust emissions of automobiles. This is done by using a platinum catalyst which converts poisonous gases to non-poisonous ones. But the catalyst, Pt, is poisoned by the presence of lead in the fuel. If the lead is completely removed from the fuel, the problem of knocking would be back. Now-a-days the auto industries are reducing knocking by lowering the compression ratio of the new automobiles being built and by increasing the octane number of fuel through changes in hydrocarbon composition, ie., by increasing, branched hydrocarbons through isomerisation. Due to the pollution caused by lead from exhaust of mobiles the lead free fuel is being made available now. . Isomerisation. Isomerisation is employed in reforming straight chain hydrocarbons into branched chain hydrocarbons: This makes them as better fuels. This is done by the reaction of strong Lewis acid catalysts which rearrange straight chain alkanes into branched-chain alkanes. Thus in the presence: of AICl, + HCl, n-butane is converted reversibly into isobutane. Hj— CH—CH,—CH, —= CCH —cH, CHg 20% 80% 8. Catalytic cracking, It is the major industrial process which is directed towards the production of fuels. This is done by bringing into contact high boiling petroleum fraction with finely divided silica-alumina catalyst at 500°C and under slight pressure. Catalytic cracking not only increases the yield of the motor fuel but also converts higher into highly branched alkanes (isomerization) which improves the quality of AL0Os / SiO2 CiHag Oe 2CsHyo + CH + C3Hy 9. Catalytic reforming. In catalytic reforming enormous quantities of aliphatic hydrocarbons are converted into unsaturated hydrocarbons, which are used as better fuel. A huge number of important chemicals are derived from benzene, Therefore chain alkanes are converted into aromatic compounds by the pres "elorming. For example eS raped aah avr CHa q Revae ALO. 5 Ftcatyat benzebe’ “2 The process of converting oj chain, “omatization, Pen chain, alkanes to benzene is also calledro) Organte Chenniatty - ton of alk nea can be selectively dehy erate a Deny atalyats whieh bring, about dehydroge tn rogenation . te pre ee whieh pyrolyels oceurs, The catsly a ee ast osenton a \ A alkanes are otter of ehromluny Pr ae A afin een ve nebutane to butener taken place at go. n00"e 1 the presen catalysts ; _» CHyse CH CHy—CHs fbutene catalyat . 7 “ Z CHyCH,CHQCHy ——+ Cl iy CH RCH ~CHy “nebutane _-» CH, == CH CHS CHy {Bbutadiene This reaction is of great commercial Importance because the product, butenes and butadiene, are useful material for petrochemical industry, and gasoline manufacture. CYCLOALKANES Cyelic hydrocarbons having C—C and C —H bonds like those of alkanes but geal — ike that of alkenes CyHgn are known as cycloalkanes. A cycloalkane may be theoretically assumed to be formed from an alkane by removing two hydro} = oe two carbon atoms of the chain and linking these ease one ater a5 5 Phi ee of ae are like the properties of alkanes, while some of e small ri . strained cyclic ring which resemble Hee hve epecial proper — Nomenclature Cycloalkanes are : ee named by prefixiny ine having the same number of ehcbon Mesa tien mare ¢ of - corresponding . imple: H, HC a oon WEG HC Neu : ne - bu, H. t. f P fi cyclopropane 2 cyclobutan Substituents on the ring are named ee , cyclohexane number 1's amsignad too hen positions og are napibered by Sa carbon of the Rapauiicens by numbers, Positio® i either clockwise or counter te other carbon atoms of t wise around the ring !*Allphatic Hydrocarbons 104 such a way as to give the lowest combination of numbers to the substituents For example: CH3 CH3 CH, De OA ‘CH, methyl 1,2-dimethyl cyclobutane 1, 3-dimethy] cyclopropane (not 14-dimethyl cyclohexane cyclobutane) For convenience cycloalkane rings are often represented by simple, geometrical figures, ie., a triangle for cyclopropane, a square for cyclobutane, a pentagon for cyclopentane, a hexagon for cyclohexane and so on. It is understood that two hydrogens are attached to each carbon atom present at each corner of the figure, therefore, hydrogens are not shown in the structure. A group other than hydrogen is invariably indicated in the structure. For example: Hs CH3 CHs cyclobutane ethylcyclobutane —_1,-dimethyl cyclopentane CHg cyclohexane CHs 14-dimethyl cyclohexane ie i De Lethyl-4-(1,1-dimethylethyl) 16-dimethyl (-methylethyl) cyclohexane cyclohexene : cyclopentane Bicycloalkanes and spiranes “pe A bicycloalkane contains two rings that share two carbon atoms in common. The shared carbon atoms are called bridgehead arbons and thé ‘onnectin; them are called bridges. The general formula of a bicycloatkane st ree a 7 like Common and IUPAC names of bicyclo alkanes are given below. ae 1 5 3 (norbornane) Bicyclo [2.2.1] heptane102 Organic Chemistry pon atoms around the i! ket number of car’ ‘a t : is written in brac | of catbon ern het tng bi at ene to lower number. The un ake at dee on right side @ 0 Land 4. bon number , Sea too: Hee ree gan and has one avon Other examp and 3) an‘ are ana Bicyclo [4.3.0] nonane : ‘ (Hydrindane) 4 Bat 5 Bicyclo [4.4.0] decane and (Decalin) Bicyclo [2.2.2] octane (Bornane) Preparation of Cycloalkanes 1. Freund Synthesis Dehalogenlation of dihalides. 1,3 or 1, 4-Dihalides may be used to prepare small ting cycloalkanes. The reaction is carried out using Na or Zn when one halide is Converted into organometallic compound. Subsequent elimination of metallic halide " gives cycloalkane, With Na yield is poor. This reaction is known as Freund synthesis. CH,Cl oa CH,ZnCl CH, CH, A ond —— > HC¢ | ‘CH,Cl ‘CHCl Ncu, cyclopropane CH)—CH,Br sz, CH, CH, plOproPs ae CH, —CHyBr | | cyclobutane i CH,—CH), a 22 SimmonsSmith reaction Cyclopropane may also be prepared by treating pl ethane in the presence .of Zn-Cu couple. The mechanism involves 4 complex, which adds to the x bond to give cyclopropan ae CHyL, + Zn ——> CH ...., Znly Hien : carbene compl CH, = CH) +CH, eae a oo as 3. Diels-Alder rea CH, compounds to yelic cor thermal addition of a epee is the Diels Alder re: butadic unsaturated group Examples ao to an olefinic double — Ce 13- : butadiene maleic anyhdride cyclohexene derivative + Zn, ction, A useful reaction which can convert open chain an The reaction involves ond preferably attached to a"404 Organic Chemistry OH Cfl(OH +342 “35 atmosphere cyclohexanol phenot Physical Properties ; ns Cyclopropane is a gas while cyclobutane Cyclopentane boils at 49°C ‘and the boiling poin! boils at 210°C. idly so that cyclodecan ‘ ee kanes and alkenes cyé ‘As compared to al ‘Thus cyclohexane, r-hexan and higher densities. ca 1 respectively 81°C, 68.8°C and 639°C, and specific gravity ww boiling liquid (bp. 12°C). is a lo 2 alkanes rise rather ts of higher cyclo: Joalkanes possess higher boiling points e and 1-hexene have boiling points of 0.7787, 0.6504 and 0.6736 Juble in water and soluble in respectively. Like other hydrocarbons, cycloalkanes are insol alcohol and ether. Structure of Small Ring Cycloalkanes ies, of which cyclopropane is the The cycloalkanes form a homologous sen smallest member. The higher members are cyclobutane, cyclopentane, cyclohexane and so on. Rings which contain 3 or 4 carbons are called small rings, those containing 5 to 7 cerbons are referred to as common rings, while those containing 8 to 11 carbons are medium rings. Rings containing 12 or more carbons are termed as large rings. The common and large rings are sintlar to alkanes in almost all of their physical and chemical properties, whereas ‘both the small and medium rings behave rather differently. : a ‘The unusual behaviour of small rings stems from the fact that the sp3 carbon fends to have bond angles near the tetrahedral value, ie., 109.5°, while the geometric reuemens ofthe smal ings rece these angles to much smaller.values. angen orbitals on the same carbon have an angle of 90° between them. If these nas a ypadined by adding s character to them, the angle between them increase Te ° oe M 2 - 180° when the amount of s character reaches 50% (sp"— 1095 , sp = 180°). There is ‘i os lo not have their bonding orbitals | ’. This_means. that in cyclopropane carbon-carbon bonds are best described pointing directly at one another, and the ed as bent. Such bonds are not as strong % ordinary bonds, and such ary bonds, a molecule has hi molecule ofthis type are said to besrained malian ee High ay ae em ae that the C—C—C inter rere overlap of pure p orbitals then the result mn the resultin, ig bond would be ver ie ry weak. addition of some s character ch makes them gtr. ne and cyclobutane have bent bonds and are high ee tron collinealy TRiis cyclopropan? IY Seine ee angles in cyclobutane, (90°), af Baeyer's Strain Theory According to Baeyer’s Strai stable. The stabili ain Theory, a molec i sable, The 7 ity of eycloalkanes canbe Paes is more strained is let : ee group. The heats of combusti y measuring the heat cycloalkanes are given below (Table 3.3), stion per CH, group for somAliphatic Hydrocarbons 105 Table 3.3 Cycloalkane Heat of Combustion per Deviation of valence angle CH, group / kj mol from tetrahedral angle Cyclopropane 705 moe Cyclobutane - ae oe Cyclopentane a oe Cyclohexane = ae The heat of combustion per CH; group decreases upto cyclopentane, showing that the stability of the ring is increasing. This is in accordance with the deviation of valence angle from the tetrahedral. For cyclohexane onwards the heat of combustion per CH, group becomes practically constant showing minimum angular strain, although the angular deviation as calculated by assuming planar tings, is increasing. The reason for no angular strain in cyclohexane and higher rings is that the rings are puckered and the angle between C — C bonds is tetrahedral. Thus only the small ring cycloalkanes have angular strain. Bent structure of cyclopropane and cyclobutane are shown in Fig, 3.1 ec» @ . naa an ts Ce Fig. 3.1. (a) bent structure of cyclopropane (b) puckered structure of cyclobutane Reactions of Cycloalkanes ‘The reactions of cycloalkanes are of two types. Reactions in which cycloalkanes resemble alkenes and those in which they resemble alkanes. = ‘Small ring cycloalkanes undergo chemical reactions which lead to the rupture of the strained system to release their strain. t Examples that show behaviour of small ring cycloalkanes which resemble that of alkenes. 1 Isomerization. Cyclopropane'is like propene as it isomerizes to propene on heating. i ——— CH3;—CH=CH 2. Catalytic hydrogenation. Cyclopropane gives propane on hydrogenation with Nias a catalyst at 80-100°C, whereas cyclobutane gives n-butane at 100-200°C, showing, thot eyclopropane is under nvice strain than cyclobutane, This reaction of cyclopropane and cyclobutane is similar to that of propene and butene, x NiorPt Gy, . Ha cegeone oat age 7 iN +H wow (CH3 — CH) — CH) —CH3 3. Addition of hydrogen halide. Hydrogen bromide, adds to cyclopropane to give n-propyl promide and to methyl cyclopropane to give 2-bromobutane inAllphatic Hydrocarbons 107 ALKENES AND ALKYNES ALKENES Alkenes, general formula C,H,,, are another famil with two hydrogen atoms:per molecule less than the corresponding alkanes. For this reason alkenens are called unsaturated hydrocarbons. An alkene can therefore be converted to the corresponding saturated hydrocarbon, an alkane, by agdition, of one molar equivalent of hydrogen. ly of aliphatic hydrocarbons The first member of alkene series has the formula, C)Hy, and is commonly known as ethylene. Each member of alkene series has one carbon-carbon double bond in their molecules to satisfy the fourth valency of carbon. Nomenclature of Alkenes The first few members of alkene series have common names like ethylene (CjH,), Propylene (C,H,) and butylene (C4Hg). The higher alkenes are generally named by the TUPAC rules which are discussed below. 1. Select the longest continuous chain that contains both the carbon atoms of the “double bond. The parent name of an alkene is then obtained by changing the ending-ane of the corresponding alkane to ene, eg. CH,=CH, CH;—-CH=CH, ethene "propene 2. Number the carbon atoms of the continuous chain from that side which. gives the two doubly bonded carbons the smallest numbers. The position of the double bond is aicsted by putting the number of lower numbered carbon of the double bond before thename of the alkene, CHs~CH,~CH=CH, , CHs~CH,—CH=CH—CH, cee er es 2 al Bye Ai dig® 52, 41, 2-pentene or pent-2-ene Is indicated by the suffix-diene for soon. 1-butene or but-1-ene 3. Preseni fio, a ‘ce of more than one double bonds bonds, triene for three double bonds and CH,=CH—CH = CH, 1,3-butadiene or buta-1,3-diene When a geometric isomer is to be specified, a prefix cis of trans is added. Gare =r oe HOH cis~2-butene108 Organic Chemistry Preparation of Alkenes be obtained in the laboratory b on known as elimination. In yy a reacti i olecule by removing atoms an sinioton react ‘a double bond is introduced into am or groups from two adjacent carbon atoms, erat elimination ee eal -AB ae ‘There are three ways by which an elimination reaction may lead to an alkene, These are, (i) Dehydration of alcohols. + (ii) Dehydrohalogenation of mono alky! halides and (iii) Dehalogenation of vic-dihalides. : 1. Dehydration of alcohols. Alcohols may be dehydrated to alkenes by heating alone between 400-800°C. However, when vapours of alcohols are passed over heated alumina, which is used as a catalyst, dehydration occurs at relatively low temperature, thus pri-alcohols are dehydrated at 350°C, sec-alcohols at 250°C and tert-alcohols at 150°C. Primary alcohols may also be dehydrated in the presence of concentrated sulphuric acid used as a catalyst, at 170°C while secondary and tertiary alcohols are dehydrated by hot diluted sulphuric acid. concH,SO, ' CH,CH,OH “S24 CH,=CH, CH. 60% S04 a OH oes SC ie cH, 20%HSO, oS CH;—C— OH 2904, Es Death Hy ease of dehydration is therefore, tert > sec—> pri-. Phosphoric acid, H, ; ayaetaat SPO4, may be used in place of sulphuric acid to avoid Primary alcohols with long chains may gen shift cor wi undergo hyd ift, whi alcohols undergo change in carbon skeleton duty cei awe ae gies conc. H,SO, (CH;CH,CH,CH,OH —“Type—$ CH; —~CH,—CH = CH, + CH;—CH = CH—CH. “a 3 1-butanol 1-butene cis and trans 2-butenesI : Aliphatic Hydrocarbons 1 13 5. Wittig reaction. Wittig reaction involves the preparation of Phosphonium ylide known as Wittig reagent, which when treated with a carbonyl compound, i., an aldehyde or a ketone, provides an excellent synthetic method for the preparation of alkenes. It is carried out in three steps. : (i) Formation of tripheny! phosphonium halide. Tripheny| phosphene is mixed with a primary alkyl halide to give triphenyl phosphonium halide salt. (CeHy)gP + CH3l > (CoH) PCH,T methyl triphenyl phosphonium iodide (ii) Formation of ylide. This salt is treated with n-butyl lithium in dry ether to remove a molecule of hydrogen halide and to give triphenyl phosphorane, the ylide. > n-butyl Li (Cetis)sBCHGI “Fyche? (CéHs)3 P= CHa ylide (triphenyl phosphorane) The ylide or the Wittig reagent is resonance hybrid of the following structures. (CHg)3P = CH — (C,H); P* —CH> __ (iti) Reaction of ylide with aldehydes or ketones to give alkene. The ylide is not isolated and is treated with an aldehyde or a ketone to give an alkene through a four centered transition state, 2 (C.Hs); P-7-=CH, eid. Qo — | bE (CH5),;PO + (\cu, Akane lene , Doneeas Physical Properties that are essentially the same as those of the thes or eee _ water, but quite soluble in non-polar solvents like pong Points rise wih Ha They are less dense than water. As shown in Table 3.4, the a se ig ae : ‘asing carbon number, and as with the alkanes, the boiling Pointy degree for each added carbon, Branching, however, lowers the boiling bing, Alkenes are Ate easily pulled a weakly Polar, since the loosely held electrons of the double md * descne led or pushed. f Pt | Dipole moments are lai in Tom alkyl group to the do ly bonded aac than for alkanes and are Phyical Properties114 Organic Chemistry 34 = Relative MP. BP. Density Formula °C °c g/cm? Name -169 102 i =CH, Ethylene CH; =CH2 =; ae . Propylene CH;=CH—CH3 . 9 e 1-Butene (CH)=CH—CHy—CH3 Bs Ae 1-Pentene Cly=CH—CHr—CH—CHs 138 64 0.675 1-Hexene CH= CH~{CHy)s —CH3 ee 1-Heptene CH=CH{CHa)¢—CHa ine i ae 1-Octene CH)=CH (CHp)s—CHs ei te a _ ee L . 1-Nonene (CHp=CH—{CH2)g—CH3 ie 1-Decene CH)=CH{CHp)7—CH aS, : CH;—C =CH—CH a a : cis-2-Butene | | ; HH i trans-2-Butene CHy—CH=C—CHy -106 -1 7 H Isobutylene CH= C(CHg)2 141 7 7 cis-2-Butene, with two methyl groups on one side of the molecule and two hydrogens on the others, should have a dipole moment. In trans-2-butene on the othet hand, with one meth moment should be zero. ca a I af Na cis~2-butene, bp.+4c Mp. ~137C dipole moment expected 0 ‘A= di Cc Il 7 trans—2-butene bp. -19C ™p. ~106°C ipole moment not expected yl and one hydrogen on each side of the molecule, the dipole _Allphatic Hydrocarbons 115 Although the dipole moments have not been measured directly, a small difference in polarity is indicated in the higher bp. of the cis-isomer and beenuse of its lower symmetry it fits into a crystalline lattice more poorly and thus has the lower melting point. Reactions of Alkenes The characteristic feature of the alkene structure is .the carbon-carbon double bond. The portion other than the carbon-carbon double bond in alkene is the alkyl group. The reactions of alkenes are therefore of two kinds, first, those reactions that take place at the double bond and destroy it, i, addition reactions, and those reactions that take place.on alkyl part of alkene leaving the double bond in-tact in the product, ice, substitution reactions. By selecting suitable conditions and reagents it is possible to control the reaction of alkenes to be addition or substitution. Before discussing the reactions, let us look into the nature of carbon-carbon double bond. As has been discussed in chapter 1 a double bond consists of a strong o bond and a weak m bond. The 1 bond has a cloud of electrons above and below the plane of the atoms as shown in Fig. 3.2. — a Fig. 3.2 An bond These m electrons are less involved in holding together the carbon nuclei than the o bond. The loosely held 1'electrons are more exposed to external Teagents and are, therefore, evallable to attack by an electrophilic reagent. Thus a double bond acts as a nucleophile, ‘6, an electron donating species. Therefore, the compounds which are deficient in electrons, i.e, electrophiles or acids would react with an alkene. The typical reaction of is thus, electrophilic addition. Free radicals also seek an electron which is Provided by an alkene double bond, so alkenes also undergo free-radical addition. Besides the addition reactions, alkenes undergo substitution in the alkyl portion. Addition and substitution reactions of alkenes are given below. ; 1. Hydrogenation, The reaction of an unsaturated compound with hydrogen gas in the presence of finely divided metal catalyst to give a saturated compound is called ‘atalytic hydrogenation. In classical method of hydrogenation a solution of an alkene is under, a slight pressure of hydrogen gas in the presence of a small amount of the Satalyst. Reaction takes place rapidly and when it is completed the solution of the Sturated product is simply filtered from the insolublecatalyst. This type of reaction is Called heterogeneous itydrogenation or two phase hydrogenation. With soluble organic intPlexes of transition metals it is possible to carry out hydrogenation in one: phase ‘homogeneous hydrogenation) but this involves the difficulty of separating the soluble “talyst from the product. Hydrogenation in general is an excellent method for" pe Ikane or any unsaturated compound into the ee nd "Thus ethene reacts with hydrogen at toom p etal catalyst like an palladium i is used as PtO, Pd is employed as pow’ der supported and nickel to give re) ie Nickel cafalyst is obtained by dissolving Ni - Se aH ‘which dissolves Al leaving fine suspension of Ni. Examples below ad f hydrogen is needed to saturate a double bond. : corresponding $4 temperature an show that 7 mole o} Pt Qn # 0 cyclohexene, cyclohexane *CH2 = CHCH = CHCH)CHs + 2H2 te CH3CH2CH2CH2CH2CHs * 1,3-hexadiene nchexane Since the réaction is quantitative and thé volume of hydrogen used can be easily measured, hydrogenation can be used to find the number of double bonds in a compound. Vitamin A requires five molecules of hydrogen for complete reduction and hence has five double bonds in its molecule. An industrial applicatien of catalytic hydrogenation is the conversion of vegetable oil to hydrogenated oil which is sold as Synthetic ghee, or partially hydrogenated oil, margarine. Vegetable oil +H, catalyst (Ni) margarine Hydrogenation is i i as ue bs exothermic reaction. When one mole of hydrogen adds to4 anda nbond is broken, ©! 3” alkene two bonds (C—H) are formed and ao (HH) al —C= CH c PH Hy tae | Suppose durin ay the reacti ; bya ae oF irate AH heat is evolved. The quantity of heat evolv Fogenation cor hydrogenated is called the heat The mpound is rid ‘at of hyd; " for each double bong ix hYAt8enation of alkenes ie fairly close to a value of 120} heats of hydrogenation are giver Table 3.5. compound. SomeAllphatic Hydrocarbons 117 Table 3.5 Heats of Hydrogenation of Alkenes Alkenes Heat of hydrogenation Kj mol” (-AH) Ethylene 137 Propylene 126 1-Butene . 127 cis-2-Butene 120 trans-2-Butene 116 Isobutylene 119 1-Pentene 126 cis-2-Pentene 120 trans~2-Pentene 115 Heats of hydrogenation can give us valuable Stabilties of unsaturated compounds. For example, Pentene is 120 kj mol information aboiit the relative the heat of hydrogenation of cis-2- whereas that of trans-2-pentene is 115 kJ mol". Thus the trans~ omer is 5 kJ mol”? more stable than the cis isomer. hydrogenations of ethylene (137) with Propylene (126) and that of 1-butene (127) with ‘ras-2-butene (116) and isobutylene (119), Table 344, itis seen that increasing alkylation Stone or both ends of the double bond lead to lower values of heats of hydrogenation or Greater. Stability of the alkene. 2. Addition of halogens. When an alkene is treated with chlorine or bromine in an inert solvent like CCl a vicinal dihalide is obtained. The addition Proceeds rapidly at ‘oom temperature. Iodine generally fails to react. This reaction provides an excellent dint '9" preparing vicinal dibromides, sect ne ethylene dibromide or propylene toromide as shown is the following equations, Similarly comparing heats of cl CH=CH +p cacy Br oBr cc, CHs— CH=CH +B <4, cry — CHBr — CH)Br Pre agai decolourization ofa red solution of bromine, when it adds to an alkene to ™ mide, is used 8 a test for the detection of an alkene double bond. Nhe 's believed to be the electrophilic addition of positive bromine to give © um ion which is then attacked by the bromide ion, Br , only from the thal the iwo bromine atoms are added to the double bond opposite to each118 Organic Chemistry other. It is the trans stereochemistry of the product that has led to the concept of the bromonium ion intermediate. ‘Thus cyclohexene gives trans-1, 2-dibromocyclohexane when treated with bromine in ccy. gat CCl, 3. Addition of hypohalous acid (HOX). When halogenation is conducted in aqueous medium, halchydrin is formed in addition to the dihalide, which show an addition of hypohalous acid. HOW fo. CH)= CHp + Br, —— a — Gh (halohydrin) OH Br H, CH3—CH = CH +Ch +H,0 Ho, cH,—cH—cy OH Cl ‘These products are obtained by the same intermediate bromonium ion. + r Bee CHp=CH)+Br—Br——_5 CH) —CHp+Br - a Br B 4a HON , pC CH — Cy > Cy — CH OH bx 4. Addition of halogen acids and orientati einige — of addition. Alkenes react with CHy= CHp+HCl == cH,—d,c1 The order of reactivity of halogen acids with alkenes is HI ; i : ; HI is least reactive, It reacts with ethylene in the bee of a Suet age nels ethyl chloride.122 Organic Chemistry cH OH CH; + | H,O | l a c—C—CH --CHy bi CH; unexpected alcohol 7, Hydroboration. Alkenes react with diborane, BaH or (BHa)2, in THE, at room temperature to form trialkyl boranes, RsB, which on oxidation with alkaline Terminal alkenes give primary alkyl boranes whose hydrogenperoxide give alcohols, oxidation leads to an anti Markovnikov's product. For example: chy ct= a, ES, xc CHB 4 H,O.+OH™ (CH;CH.CH_OH 2 n-propyl alcohol Similarly the diborane reacts with 3, 3-dimethyi-1-butene to give exclusively, an anti Markovnikov’s product, which is different from the product formed by oxymercuration ~demercuration procedure. i Hs GeG_-ci—-a, OR a. bo oO pmonntp, <— Fh_—Ch OH cH, 3. 3-dimethy-1-butanolAliphatic Hydrocarbons 123 CHy—CH= cH, Peracid Gy, ro $i ‘° epoxy propane Fpoxides also called oxiranes are unstable compounds and are used as intermediates for the preparation of higher alcohols. (ii) Hydroxylation. Cold dilute solution of potassium permanganate reacts with a double bond to give vicinal diol, which is commonly called a’glycol. The reaction is jnown’as hydroxylation. The solution of KMnO, is decolourized during hydroxylation, therefore, this is also used as a test for the presence of unsaturation. KMno, Hy =CH, ————*» CH) — CH OH OH glycol © The reaction occurs with cis addition and is thought to involve an intermediate cyclic manganate ester that is rapidly hydrolyzed to cis diol. dil KMnO, CH — CH=CH — CH Cs — C= A CHs p Ad ZEN -O O LH,O CE a eee OH OH cis-doil foe or’ Same overall reaction can be accomplished with osmium tetroxide, which ‘ons ‘solable cyclic ester with alkenes. The cis-diol can be isolated from the osmate ester With either HS or HzO>, With Hj, Os70s is regenerated. "CH= CHR +050, thet, R-CH—CH-R cal tas adele | | QO OH OH Ve ie \ osmate ester ; (id Cleavage of double bond, A cs-diol can further be oxidized through cleave ¢ 4 with reagents like POAC), or HIO,, A concentrated acidic and hot solu! i es, 4 May also oxidize further, the initially formed glycol, © give two KEN" * re ofthe nd a carboxylic acid, or two carboxylic acids depending upon the Kitno, tu! igh, The ms struct Feaction is known as the oxidative cleavage of the double bone:Allphatic Hydrocarbons 127 Alkynes constitute another famil formula C,H),»; thus each member of alkyne family has two atoms of hydrogen fewer than the corresponding member of alkene family and conse uently alll alk triple bond in their molecule, : eens conan 9 The common name of the first me molecular formulae CjH, and has linear s bond and two m bonds as shown in Fig. 3.3. mber of the alkyne series is acetylene, It has tructure HC = CH, which consists of a ¢ ve \e formation of 4 ; ~ saan i o H— cil + Se,o—_ AA 1m pytpy and 1 pot pz Nomenclature ? ‘The simple alkynes are named in the common system as derivative of acetylene, eg, CH; —C=CH CoHs—C=C—GH, Methylacetylene diphenyl acetylene In the IUPAC system these hydrocarbons are name d as alkynes by replacing the final ~ane of the Parent alkane with the suffix-yne. The position of the triple bond is indicated by a number. For example: CH, —CH,—C=CH is 1-butyne 4 3 2 1 CH;—CH —C=CH is 3~methyl-1-butyne. | . cH, When both a double and a triple bond are present, the hydrocarbon is named as Sn alkenyne with the lowest Possible number given to the triple bond, ie,, CH3—CH=CH—CescH is 3-penten-1-yne, and not 2-penten-4-yne . When both multiple bonds are at 1 position, the double bond gets the lower “ber. Thus HCasc_ CH,CH =-CH, is |-penten-4~yne and not -pantensdeyne. Physica) Properties tr responding Physical ies of alky imilar to those of the correspon Properties of alkynes are simi eon the “Met, The lower members are Bases with boiling points somewhat higher than128 Organic Chemistry corresponding alkenes. Terminal alkynes have lower b.p. than isomeric alkynes, ie 1~butyne (b.p. 8°C) and 2-butyne (b.p. 27°C) as shown in Table 3.6. Table 3.6 Compound MPC specific gravity Ethyne -81 eS Propyne -102 - 1-Butyne 8 -12 - 2-Butyne a7 -32 - 1-Pentyne 39 -90 - 2-Pentyne 55 101 - 1-Hexyne 7 | -132 0.7152 2-Hexyne 84 -88 0.7317 3-Hexyne 81 -105 0.7231 Preparation of Alkynes 1. Dehydrohalogenation of geminal or vicinal dihalides. Acetylene or hight! alkynes may be prepared by heating a gem-dihalide or vic-dihalide with alcoholk solution of KOH. 1-Alkynes are usually not stable under these highly basic conditions Therefore, wherever possible a triple bond may migrate along a chain to give more stable disubstituted alkyne. KOH CH,—CH— —_—, —C= Hy mf ce zi 7 CH,;—C=CH Br Br I-propyne vic-dihalide KOH CH) — CHBr, KOH , pai ©>- 2 "2FIcohol ©- =cH gem-dihalide cH,—cH—cH—cu, KOH | ] “aeoho? Hs — CH, — C= CH Br Br Ua butyne