14.14 Cycloalkanes ar formula CyFlay- They are eral molecu Tethods of preparation of Cycloalkanes are cyclic analogues of alkanes. They have the gen toms. A few meth isomeric with alkenes (CyHg,) with the same number of carbon a! cycloalkanes are outlined below. 11.14.1 Preparation of Cyclopropane to form cyclopro- 1. 13-Dibromopropane reacts with sodium in anhydrous diethylether or tetrahydrofuran to form cYCoP! pane, EO Br A ona Be J +2NaBr heat 1,3-Dibromopropane Cyclopropane This is an internal Wurtz reaction. The cyclisation can be effected more efficiently by heating with zinc in ethanol (Freund synthesis). Br. Br BIOL NB an BEE ZA +2 2. Alkenes undergo addition with carbene (CH) to form cyclopropane ring. Carbene is generated from diazomethane by thermolysis or photolysis. heat or (CH=CH + CH2Nz ~~ jy VV +No 3. Alkenes react with methylene iodide (CHglp) in the presence of zinc-copper couple to form cyclopropane ring. This is called Simons-Smith reaction. At first, CHylp reacts with zinc to form the Simons-Smith reagent ICH,Znl (an organometallic compound) which has carbene-like reactivity and is called a earbe- noid. The reagent delivers carbene to be adcled to carbon-carbon double bond to form cyclopropane ring CH=CH + CHyly + Zn-Cu —+ CHy—CH, + Znly + Cu \Z CH 11.14.2 Preparation of Cyclobutane 1. 14-Dibromobutane on being heated with zinc in ethanol forms cyclobutane in a low yield Br +Zn ao +ZnBry pa eat 14-Dibromobutane CyclobutaneAlkanes and Cycloatkanes 337 2, Alkenes undergo photochemical [242|-cycloaddition to form cyclobutane ring. Ethylene Cyclobutane (two molecules) bw. With 1,3-dibromopropane and diethyl malonate, cyclobutane can be prepared as follows: @ (E10,0),CH, + FIONa —> —(E10,€);CHON® + EOHT Diethyl malonate Diethyl sodiomatonate Br ee = Nabr, Br ELONa_ CR oe +Na* CH(COzEt), Ge coy, C(CO2Et),Na* | NaBr AgOH heat .CO2H _1. KOH, heat COLE <>—cooag <0 BO tnt << COE Br] CCl, heat << Mate BOS mgtonnee 11.14.3 Preparation of Cyclopentane ‘lopentanone can be prepared by strongly heating calcium or barium salt of hexane-1,6-dioic acid, also id adipic acid (Piria method). Cyclopentanone can be converted into ¢ -yclopentane by Clemmensen uae. ‘COO ay distillation ° Zn-Hg coo- = BaCOs 7 cone. HIG), heat Barium adipate | Cyclopentanone Cyclopentane 1 adipate when treated with sodium ethoxide undergoes Dieckmann condensation (section 19.8.4(c)) 'm ethyl 2-oxocyclopentanecarboxylate. The latter is converted into cyclopentane as shown. EIONa, ap HCH. Zn-Hg a C deco a CSc aoe. aa ° ° ° | 3. 1,5-Dibromopentane when heated with zinc in ethanol gives cyclopentane in a poor yield. EtOH, Br: BrChemistry of Organic Compounds 338 14,14.4 Preparation of Cyclohexane aly tic hydrogenation of bi Ni, 150-250°C +3Ha 25 atm Cyclohexane enzene: 1, By ea Benzene 2. By the application of Diels-Alder reaction, [4+2]-cycloaddition: ‘COOH COOH A ‘a treat Cy Cr NaOH (C30), * . leat ~ Diels-Alder reaction tae13ediene Propendi Cyelohex-d-ene- Cyctohexane- pnd aaa carboxylic aid carboxylic acid Yelohexane yf application of Dieckmann condensation of ethyl heptane-1,7-dioate (ethyl pimelate): ° “OE COE ci/tti0 b> Eon HCHO _Zotig CORY BOH Theat TACT heat” reaction of cyclopentanone with diazomethane: __ 2retig 0 + CHNy > “cone. HCI, heat” ns of Cycloalkanes 11.15 React 11.15.1 Addition Reactions Cyclopropane and cyclobutane suffer from severe angle strain (section 9.7.7). They are relatively unstable and very reactive. They undergo addition reactions with Hg (in presence of Ni catalyst) and some electrophilic reagents such as Cly, Bry and HX. Cyclobutane has less strain and therefore reacts relatively sluggishly. Cyclopentane and cyclohexane are stable molecules and do not undergo addition reactions. (i) Addition of hydrogen (CH)—CH2 Ni CH: Ia +H, Ni, J F NL, A 2 “BOC” Ci; Cy * +H So0°¢ ce CH Cyclopropane Propane cyclobutane Butane (ii) Addition of chlorine and bromine LV +e, SS NG LX +b ABS ee Cyclopropane 1,3-Dichloropropane Cyclopropane 1,3-Dibromopropane Alby +B Tegel Lx Cyclobutane 1,4-DibromobutaneManes and Cyctoatkanes 339 Addition of hydrogen halides and sulphuric acid CU: Cup +HBr ——. 2 +H - we S, A Ao tccine A eer HySO, CHa £\ +H sO, ——+ Cg /\ +H,0 Pi ae ay Me Lobos 2 Ch, ~CHLOH Cyclopropane n-Propyl hydrogen Cyclopropane Propan-I-ol sulphate 11.15.2 Free-Radical Halogenation (Substitution) Like alkanes, cycloalkanes undergo free-radical chlorination and bromination in presence of light or heat. A few examples are given below. Br L tm Aca saa + Br, + HBr Cyclopropane Chlorocyclopropane Cyclobutane Bromocyclobutane +09 dese, C7 +NBr O +a, Cy +H teenie fehl epeieioy on Chlorocyctohexane 11.16 Structures of Cyclopropane and Cyclobutane The cyclopropane ring is planar. The intemuclear C—C—C bond angles are 60°. The C_C—H and H_C—H bond angles are 116° and 118° respectively. All of the bonds are eclipsed in cyclopropane. The carbon atoms of cyclopropane are not exactly sp? hybridised. Two of the four hybrid orbitals of carbon has more p character (~80% p) than expected for an sp* orbital (75% p). These two hybrid orbitals behave as if they are sp® orbitals. The other two hybrid orbitals have less p character (~65% p) than expected (75% p) They behave as if they are almost sp? orbitals. The two C—H bonds of each carbon atom are formed by these sp* orbitals with 1s orbital of hydrogen atom (linear overlap). The C—C bonds in cyclopropane are formed by the overlap of the two sp* orbitals of the adjacent carbon atoms. The geometry of the ring is such that these orbitals cannot overlap linearly, rather they overlap at a slight angle. So, the electron cloud of the C_ C bond is not concentrated around the internuclear axis, rather strongly displaced outward from the internuclear axis. Hence, the C—C bonds of eyclopropane are bent in a banana shape around the periphery of the ring, For this reason, these bonds are called bent bonds or banana bonds. Since the overlap of the sp* orbitals are neither linear as in ¢ bonds nor lateral as in x bonds, but subtends an angle, these CC bonds arecalled + (tau) bonds. Thus, the interorbital C—C—C bond angle is about 105°. This reduces the angle strain but at the same time decreases the strength of C—C bond. This decreased strength of the C__C bond and the angle strain together explain why cyclopropane undergoes addition reaction like an alkene, H | 109 pm c lipsea PV Ne J ectps HL Moy Ne sete H7 SIP EA jg HH Hy H H/ eclipsed Geometry of Newman projection of, cyclopropane molecule yelopropane Formation of C—C bent bond in cyclopropane by: orbital overlap (neither linear nor lateral but at some angle); the dashed lines show the bent bondsbe Chemistry of Organic Compounds atoms in the ring is bent out of the plane of the other Jear C—C—C bond angle of 90° tobe reduced to 85 ‘This puickering of the cyclobutane ring avoids complete eclipsing of the hydrogen atoms on adjacent carbon atoms. The orbitals that overlap to form CC ‘bond has higher p character than expected for sp? orbital In cyclobutane also, the overlap of the orbitals in C—C bond formation is not linear. So, the CC bonds in cyclobutane are slso bent bonds but the extent of bent is not as much as in cyclopropane, Cyclobutane consists of two puckered conformations in rapid equilibrium as shown below. Cyclobutane ring is not planar. One of the carbon three by about 25°, This causes the expected internuc H H H H 4 H FS ei H ; o po Sil y (77 sot quteedped Puckered conformations of cyclobutane, in rapid equilibrium Newman projection of cyclobutane HH \\Not quite ectipsec a