Enrichment XIl CBSE CHEMISTRY 10. Haloalkanes and Haloarenes The replacement of hydrogen atom(s) in a hydrocarbon, aliphatic or aromatic, by halogen atom(s) results in the formation of alkyl halide (haloalkane) and aryl halide (haloarene), respectively. 1. They are used as solvents for non-polar compounds and as starting materials for the synthesis, 2. Chloramphenicol antibiotic produced by soil microorganisms - typhoid fever. 3. Thyroxine hormone the deficiency of which causes a disease called goiter. 4. Chloroquine is used for the treatment of malaria; Halothane is used as an anaesthetic during surgery. 6. Fully fluorinated compounds are being considered as potential blood substitutes in surgery. Classification: 1. Monohaloalkanes / Monohaloarenes: They contain only one H3C—CH2-CH, Cl halogen atoms in their structures Primary: Halogen attached carbon contains one alkyl group. H3C—CH,-CH,Cl Secondary: Halogen attached carbon contains two alkyl group. HyC-HC—CH, cl Tertiary: Halogen attached carbon contains three alkyl group. 2. Dihaloalkanes/ Dihaloarenes: ‘They contain two halogen atoms in their structures Germinal: Two halogen atoms are present on thé Same carbon atom. Vicinal: Two halogen atoms are present on the adjacent carbon atom, H2G—CH2 a 3. Trihaloalkanes/ Trihaloarenes: They contain three halogen CI—CH,CH—CH, Cl atoms in their structures. cl ‘On the Basis of sp’ of hybridisation Vinylic halides: These are the compounds in which the halogen atom | HjC—=CH-Cl is bonded to a sp2-hybridised carbon atom ofa carbon-carbon double bond(C =C). Aryl halides: These are the compounds in which the halogen atom is bonded to the sp2-hybridised carbon atom of an aromatic ring Allylic halides: These are the compounds in which the halogen atom ‘CH-CH,-Cl is bonded to an sp3-hybridised carbon atom next to carbon-carbon double bond (C=C) Benzylic halides: These are the compounds in which the halogen git atom is bonded to a sp3-hybtidised carbon atom next to an aromatic 4g" SH ring. ne get Rules for 'UPAC Nomenclature I. Indentify parent chain. *Parent chain must contain principal functional groups. “If the ring contains more or equal number of carbon than the alkyl group, ring as a parent. 27Enrichment XIl CBSE CHEMISTRY *Parent chain must contain more number of carbons and more number of branches. 2. Numbering the Parent chain. *Numbering start from functional if it contain carbon or start from one end to other end of carbon chain with principal fimetional groups always in lowest number. Then applies Lowest set of locates rule and Alphabetical order numbering, Secondary primary Root word Primary suffix | Secondary suffix prefix prefix Secondary cyclo Meth,eth,prop,cct [ane,ene,yne,enyne, | principal funetional groups diene,diyne functional groups Priority functional groups: -COOH, ~SOsH, -COOR (R=alkyl group), COCI, -CONH:, -CN,-HC-O, >C=0, -OH, -NH2, > C<,-C=C- Prefix substituent:R, CoHs-, halogens (F, Cl, Br, I), -NOs, alkoxy (OR) ete. ‘Compound functional groups Secondary prefix Secondary suffix Carboxylic acids | R-COOH carboxy oie acid Aldehydes R-CHO formyl all Ketones R-COR oxo -one Alcohols ROH hydroxy -ol Amines RNA; amino -aming Halides R-XIF, CL Br, I] halo) ‘Common system CH,CH- CH,CH,CH- CH,-CH-CH, a I cH,-c- cn, cH, CH, | cH, en, Isopropyl sec Buiyl tere Bucut Neopentut Haloarenes Haloarenes are the common as well as IUPAC names of aryl halides. For dihalogen derivatives, the prefixes 0-, m-, p-are used in common system but in IUPAC system, the numerals 1,2; 1,3 and 1,4 are used. Nature of C-X Bond: Halogen atoms are more electronegative than carbon, the carbon halogen bond of alkyl halide is polarised. ‘The carbon atom bears a partial positive charge whereas the halogen atom bears a partial negative charge Bond length: Increases due to increases atomic size ;C-F < C-Cl < C-Br C-Cl > C-Br >C-1, Polarity: Increases due to decreases electronegativeC-F > C-Cl > C-Br >C-I; Dipole moments: Depend with Bond length and Polarity; C-Cl > C-F> C-B>C-1; CT has more because of product of Bond length X Polarity is more. 228Enrichment XIl CBSE CHEMISTRY List of Preparation Haloalkane and haloarene: 1. From Alcohols by using following reagent. 1, Znely/HCl (Luca’s reagent) 2. NaBr+H;SO, 3. PCls 4. PCls 5. SOCh 6. Red pBry/l, 2. Using Hydrocarbon 1. From Alkane — Free Radical Halogenation (Cl, hY) 2. From Alkene a. HydroHalogenation (HBr) + Markonikov + Antimarkonikov (with peroxide) b. Halogenation(Bry/CCls) 3. Benzene — electrophilic substitution (Brz/FeBrs) 3. Name Reactions. 1, Sandmeyer’s reaction 2. Swarts reaction 3. Finkelstein reaction 1. From Alcohols: This method only for alkyl halides not applicable for the'preparation of aryl halides because the carbon-oxygen bond in phenols has a partial double-bond character and is difficult to break being stronger than a single bond. 1. Zncl,/HCl (Luca’s reagent): The reactions of primary and secondary alcohols with HX require the presence of a catalyst, ZnCl. With tertiary alcohols, the reaction is conducted by simply shaking with concentrated HCI at room temperature. Constant boiling with HBr (48%) is used for preparing alkyl bromide zn R-OH +HX —* > R-X+H,0 Mechanism —Sy]; Reactivity - 3° >2° >1° Application- used for distinguish 3 °, 2°, and 1° alcohols. 3° alcohols > turbidity immediately 2° alcohols — turbidity occurs within 5 to 10 minutes. 1° alcohols — no turbidity occur. 2. NaBr+H SOx R-OH + NaBr+H)SO,— R-Br + NaHSO4 + 120. 2NaBr+H)SO,—Na2SO, + 2HBr Hj; cannot be used along with KI in the conversion of an alcohol to an alkyl iodide as it converts KI 10 corresponding Hl and then oxidizes it to [2So, Good yields of R—J may be obtained by heating alcohols with sodium or potassium iodide in 95% phosphoric acid. 3. PCI;: 3R-OH + PX3—> 3R-X + HsPO; 4. PCls: R-OH + PXs— R-X + POX; + HX 5. SOCI -OH + SOC], R-X + SO; + HX 229Enrichment XIl CBSE CHEMISTRY Thionyl chloride is preferred because the other two products are escapable gases, Hence the reaction gives pure alkyl halides 6. Red p/Bry/Iy: R-OV —2@8%2_4 RX (X2=Bn & b) II. Using Hydrocarbon: 1. Alkane: ch uy CHsCH.CH:CH; 2", CHsCH:CHaCH2CI + CHsCH2CHCICHs Free radical chlorination or bromination of alkanes gives a complex mixture of isomeric mono- and polyhaloalkanes, which is difficult to separate as pure compounds. Consequently, the yield of any one compound is low. Fluorination is too violent to be controlled, Iodination is very slow and a reversible reaction. It can be carried out in the presence of oxidizing agents like HIO3 or HNO Reactivity -F > C1> Br >I Rate of replacement of hydrogens of alkanes is: 3°> 2°> a, Markonikov reaction: CH CH=CH + HBr — CHsCHBrCH; Markovnikov rule states that negative part of the addendum (adding molecule) gets attached to that carbon atom which possesses lesser number of hydrogen atoms. b. Anti Markovnikov addition or peroxide effect or Kharash effect CHsCH= CH; + HBr 5 CHjCH;CH,Br Negative part of the addendum (adding molecule) géf® sitached to that carbon atom which possesses more number of hydrogen atoms The peroxide effect is not observed in addition of HCI and HL. This may be due to the fact that the H— Cl bond being stronger than HBr bond, is not cleaved by the free radical, whereas the HI bond is weaker and iodine free radicals combine to form iodine molecules instead of adding to the double bond. 2. Halogenation: CH)= CH) + Bry > CH:BrCH,Br Addition of bromine in CCl; to an alkene results in discharge of reddish brown color of bromine. The eck, addition results in the synthesis of vic-dibromides, which are colorless. (This reaction used for test for unsaturated compounds). 3. Benzene: By electrophilic substitution: The ortho and para isomers can be easily separated due to large difference in their melting point. Reactions with iodine are reversible in nature and require the presence of an oxidising agent (HNOs, HIO,) to oxidise the HI formed during iodination. Fluoro compounds are not prepared by this method due to high reactivity of fluorine. 230Enrichment XII CBSE CHEMISTRY IHL, Naming Reactions: 1. Sandmeyer’s reaction: wen cl we nF NaNoy HCI cucl +Hel peers Halogen Exchange 2. Finkelstein reaction: (CHsCH, Br + Nal > CHsCH 1+ NaBr Dry acetone precipitated NaCl or NaBr formed in this reaction. It facilitates the forward reaction according to Le Chatelier’s Principle. 3. Swarts reaction: (CH,CH, Br + AgF CH,CH)F +NaBr ‘The synthesis of alkyl fluorides is best accomplished by heating an alkyl chloride/bromide in the presence ofa metallic fluoride such as AgF, HgoF:, Co or SbF Physical Properties Appearance: Colourless when pure, however, bromides and iodides develop colour when exposed to light due to formation of halogen. Many volatile halogen compounds have sweet smell. Boiling points: alkyl halide are show high bp than hydrocarbon due to polarity. Factors affecting Boiling points: Bp. a vanderwaal's force a surface area. Bp. a no, of C in straight chain Bp.a u (net dipole moment) Bp. a (1/ branched chain) Bp. a no. of halogen Bp. a. size of halogen Melting Points: Symmetrical molecules fit crystal lattice better than unsymmetrical ones. Boiling points of isomeric dihalobenzenes are very nearly the same. However, the para-isomers are high melting as compared to their ortho-and meta-isomers. It is due to symmetry of para-isomers that fits in erystal lattice better as compared to ortho- and meta-isomers. Melting point is a packing of crystal lattice. Density: The density increases with increase in number of carbon atoms, halogen atoms and atomic mass of the halogen atoms. Solubility: The haloalkanes are only very slightly soluble in water. Less energy is released when new attractions are set up between the haloalkane and the water molecules as these are not as strong as the original hydrogen bonds in water. However, haloalkanes tend to dissolve in organic solvents because the new intermolecular attractions between haloalkanes and solvent molecules have much the same strength as the ones being broken in the separate haloalkane and solvent molecules. ‘Stereo chemical aspects Plane Polarized light: Light is propagated in the form of waves. Ordinary monochromatic light is supposed to consist of waves vibrating in all planes. If such a light is passed through a Nicol prism, the emergent light is found to consist of waves vibrating in only one plane. Such a light is called plane polarised light. 231Enrichment XIl CBSE CHEMISTRY Optical activity: Certain compounds rotate the plane polarised light when it is passed through their solutions. Such compounds are called optically active compounds. The angle by which the plane polarised light is rotated is measured by an instrument called polarimeter. The phenomenon is termed as optical isomerism. *@nOr Dextro rotatory: If the compound rotates the plane polarised light to the right, i direction, itis called dextrorotatory (Greek for right rotating) or the d-form and is indicated by placing a positive (+) sign before the degree of rotation. Laevo rotatory: If the light is rotated towards left (anticlockwise direction), the compound is said to be laevo rotatory or the I-form and a negative (~) sign is placed before the degree of rotation. Molecular asymmetry: The spatial arrangement of four groups (valencies) around a central carbon is NH tetrahedral and if all the substituents attached to that carbon are different; such a e., clockwise carbon is called asymmetric carbon or stereo centre. The resulting molecule “ on ‘would lack symmetry and is referred to as asymmetric molecule, The asymmetry cu, of the molecule is responsible for the optical activity in such organic compounds Chirality: The carbon which are non superimposable on their mirror image are Ny said to be chiral and this property is known as Chirality. While the objects, which yg, a are, superimposable on their mirror images are called achiral. The two molecules are optically active. Enantiomers: The Stereoisomers related to each otlier’as non Superimposable mirror images are called enantiomers. Enantiomers possess identical physical properties namely, melting point, boiling ‘point, solubility, refractive index, etc, They only differ with respect to the rotation of plane polarised light. If one of the enantiomer is dextro rotatory, the other will be laevo rotatory. Diastereomer: Diastereomers are stereo isomers that are not mirror images of one another and are non-superimposable on one another. Stereoisomers with two or more stereo centers can be diastereomers. They are never mirror images and differ in all physical properties. They are the direction and magnitude of optical rotation. OH oH oH on HC: NH, HN cH; HC. NH, HN. CH; ch OH HO cl Ho <1 ct OH cu, cH au, cH, A 8 c D & Band C & D; Diastereomer: A with C or D and B with C or D Racemic mixture: A mixture containing two enantiomers in equal proportions will have zero optical rotation, as the rotation due to one isomer will he cancelled by the rotation due to the other isomer. Such a mixture is known as racemic mixture or racemic modification. racemic mixture is represented by prefixing dl or (+) before the name. The process of conversion of enantiomer into a racemic mixture is known as racemisation. (+) butan-2-ol. 232Enrichment XII CBSE CHEMISTRY Meso isomer: The Meso isomer has two asymmetric carbon atoms the configuration of one Cy carbon is the mirror image of the other, the net result being the molecule as a whole becomes symmetric. This molecule is said to have a symmetric plane, aN oH which divides the molecule into two equal halves. The molecule becomes us ou “achiral”, It has configuration which is super imposable on its mirror image os Retention: The relative spatial arrangement of bonds at an asymmetric centre remains same afier a chemical reaction or transformation. Inversion: The relative spatial arrangement of bonds at an asymmetric centre is not same after a chemical reaction or transformation. Racemisation: The relative spatial arrangement of bonds at an asymmetric centre is same and also not a same after a chemical reaction or transformation. cH, ¢ fr A B If (A) is the only compound obtained, the process is called retention of configuration If B) is the only compound obtained, the process is called inversion of configuration. Ifa 50:50 mixture of the above two is obtained then the process is called racemisation and the product is optically inactive, as one isomer will rotate light in the direction opposite to another. Mechanism of Nucleophilic Substitution reactions: Substitution Nucleophilic bimolecular (Sx2) 1. The rate depends upon the concentration of both the alkyl halide and nucleophile. 2. The incoming nucleophile interacts with alkyl halide causing the carbon halide bond to break while forming a new carbon-OH bond. Reactions are carried out in aprotic solvents. 3. These two processes take place simultaneously in a single step with transition state and no intermediate is formed 4. Transition state are unstable and cannot be isolated so rearrangement not possible. 5. Reaction requires the approach of the nucleophile to the carbon bearing the leaving group, the presence of bulky substituents on or near the carbon atom have a dramatic inhibiting effect. 6. The simple alkyl halides, methyl halides react most rapidly in Sx2 reactions because there are only three small hydrogen atoms. Tertiary halides are the least reactive because bulky groups hinder the approaching nucleophiles. 7. The order of reactivity followed is: Primary halide > Secondary halide > Tertiary halide. 8. Itis inversion configuration due to backside attack so optically active forms dextro rotatory become laevo rotatory vice versa. 233Enrichment XII CBSE CHEMISTRY Substitution nucleophilic unimolecular (Sy1) on, een = e+? oe cH, on segs J + Tor — 822 eHy.con HC cH, 1. The rate of reaction depends upon the slowest step; the rate of reaction depends only on the concentration of alkyl halide. 2. The polarised C—Br bond undergoes slows cleavage to produce a carbocation and a halide ion, The carbocation thus formed is then attacked by nucleophile. 3. It occurs in two steps. Step 1 slowest and reversible& carbocation formation. ‘Step II - nucleophile substitution reaction. 3. Carbocation is stable and so rearrangement possible. The stability of carbocation, greater will be its ease of formation from alkyl halide and faster will be the rate of reaction. 4, Reactivity depended with stability of carbocation, Benzylic and allylic halides show high reactivity towards the Sy1 reaction, The carbocation thus formed gets stabilised through resonance 5. The order of reactivity followed is: Tertiary >Benzylic > allylic > Secondary > Primary 6. Itis Inversion & Retention configuration so product is a mixture of two optically active forms gives racemic mixture. 7. Reactions are generally carried out in-polar protic solyents because the C-X bond breaking energy is obtained through solvation of halide ion.with the protort of pfoti¢ solvent. 8. The reactivity of the halide: R-I> R-Br>R-Cl>>R-F. As iodine is a better leaving group because of its large size, it will be released at a faster rate in the presence of incoming nucleophile. Mechanism of Elimination reactions: When a haloalkane with f-hydrogen atom is heated with alcoholic solution of potassium hydroxide, there is elimination of hydrogen atom from B-carbon and a halogen atom from the a-carbon atom. AS a result, an alkene is formed, so itis called f-climination. Saytzeff rule which can be summarised as “in dehydrohalogenation reactions, the preferred product is that alkene which has the greater number of alkyl groups attached to the doubly bonded carbon atoms.” If there is possibility of formation of more than one alkene due to the availability of more than one a- e "als one hydrogen atoms, usually one alkene is formed as the rs “tee major product. BeBase: eLeaving group Nucleophilic vs Elimination An alkyl halide with a-hydrogen atoms when reacted with a base or a nucleophile has two competing routes: substitution (Sy1 and Sy2) and elimination, Which route will be taken up depends upon the nature of alkyl halide, strength and size of base/nucleophile and reaction conditions. Nucleophilic Substitution reactions: Substitution reaction requires the approach of the nucleophile to the carbon bearing the leaving group. So smaller nucleophile will prefer to act as a nucleophile 234Enrichment XIl CBSE CHEMISTRY therefore it can easy to approach a tetravalent carbon atom. Reactivity: Primary > Secondary > Tertiary halide. Elimination reactions: Elimination depending upon the stability of carbocation or the more substituted alkene. So bulkier nucleophile will prefer to act as a base abstracts a proton rather than approach a tetravalent carbon atom (steric reasons). Reactivity: Tertiary > Secondary > Primary Chemical property List of reaction I, Nucleophilic substitution: FOR HALOALKANE. 1.1b0 4, RONa 7. KNO2 10, CH=CNa 2. Aq-KOH 5. KCN 8. AgNO) 11. LiAIHy 3. NHs 6.AgCN 9. CH;COOA IL. Nucleophilic substitution FOR HALOARENES. IIL Electrophilic substitution reactions FOR HALOARENES. 1. Halogenation 3. Sulphonation 2. Nitration 4. Friedel-Crafts reaction a, Alkylation b. Acetylation r ination reactions V. Reaction with metals. 1. with Mg ~Grignard reagents. 2. with Na a, Wurtz reaction - FOR HALOALKANE. b. Wurtz- Fitting reaction- FOR HALOARENES WITH HALOARE! c, Fitting reaction- FOR HALOARENES. I. Nucleophilic substitution A substitution reaction takes place halogen is bonded to sp’ hybridised carbon, called leaving group departs as halide ion, itis called nucleophilic substitution reaction. Ambient nucleophiles: Groups like cyanides and nitrites possess two nucleophilic centers and are called ambident nucleophiles. KCN is predominantly ionic and provides cyanide ions in solution. Although both carbon and nitrogen atoms are in a position to donate electron pairs, the attack takes place mainly through carbon atom and not through nitrogen atom since C—C bond is more stable than C—N bond. However, AgCN is mainly covalent in nature and nitrogen is free to donate electron pair forming isocyanide as the main product. Similarly nitrite ion also represents an ambident nucleophile with two different points of linkage [- O—N-O]. The linkage through oxygen results in alkyl nitrites while through nitrogen atom, it leads to nitroalkanes. 1 20: R—X +H,0— R—OH +HX Alcohol 2 aq.KOH: R—X + ag.KOH— R—OH +KX Alcohol 3) NHS: RXX + NH; R-NH2 +HX Amine 4 RONa: R—X +RONa—>R—OR +NaX Ether 5 KCN: ROX + KCN + R—CNHKX Alkyl cyanide 6 AgCN: ROX + AgCN — RNC Agx Alkyl isocyanide 7 KNO; RXX+KNO; + R—ONO +KX Alkane nitrate 8 Agno: RXX + AgNO; + R— NO; +AgX, Nitro alkanes 9 CH;COOAg: R—X + CH\COOAg + R—OOCCH, + AgX Ester 235Enrichment XIl CBSE CHEMISTRY 10 CH=CNa: — RX +CH=CNa—+ R— C=CH +NaX Alkynes 1 Lid: RAX + LiAIHy—+ R-H Alkane II. Nucleophilic substitution: FOR HALOARENES. Aryl halides are extremely less reactive towards Nucleophilic substitution reactions due to the following reasons: () Resonance effect: C—CI bond acquires a partial double bond character due to resonance, AS a result, the bond cleavage in haloarene is difficult than haloalkane a at ‘a1 — —- ayo e CO — (F— P— OG (ii) Sp2 in hybridisation of carbon atom in C—X bond: The sp2 hybridised carbon with a greater s- character is more electronegative and can hold the electron pair of C—X bond more tightly than sp3- hybridised carbon in haloalkane with less s-character. Thus, C—CI bond length in haloalkane is 177pm while in haloarene is 169 pm. It is difficult to break a shorter bond than a longer bond. of we 4 (iii) Instability of phenyl cation: The phenyl cation formed as a result of self-ionisation will not be stabilized by resonance and therefore, Sy! mechanism is ruled out. (iv) Electron rich arenes: They are electron rich arenes therefore repulsion possible with the electron rich nucleophile to approach. Additions of —NO2 group increases reactive of Aryl halides towards Nucleophilic substitution reactions because the presence of nitro group at ortho- and para-positions withdraws the electron density from the benzene ring and thus facilitates the attack of the nucleophile on haloarene. The carbanion thus formed is stabilised through resonance. The negative charge appeared at ortho- and ‘para- positions with respect to the halogen substituent is stabilised by NO: group while in case of ‘meta-nitrobenzene, none of the resonating structures bear the negative charge on carbon atom bearing the -NO} group. on Se _omsor 445K, 0) NAOH, 6238, 300 atm Sa (i) rT ne Xe, eli on on NOs (Naot, s68K vam, ON No, a Ge NO, No, No, Therefore, the presence of nitro group at meta- position does not stabilise the negative charge and no effect on reactivity is observed by the presence of -NO2 group at meta-position. 236Enrichment XIl CBSE CHEMISTRY III. Electrophilic substitution reactions FOR HALOARENES. Halogen withdraws electrons through inductive effect and releases electrons through resonance. Through inductive effect, chlorine destabilises the intermediate carbocation formed during the electrophilic substitution. Halogen withdraws electrons through inductive effect and releases electrons through resonance. Through inductive effect, halogen destabilises the intermediate carbocation formed during the electrophilic substitution. Due to resonance, the electron density increases more at ortho- and para-positions than at meta- positions. Further, the halogen atom because of it’s -I effect has some tendency to withdraw electrons from the benzene ring. As a result, the ring gets somewhat deactivated as compared to benzene and hence the electrophilic substitution reactions in haloarenes occur slowly and require more drastic conditions as compared to those in benzene. 1.Halogenation a € ‘ i SS Anhyd. FeCl, “y' Orem Os Cr 1, 2-Dichloroberzene 1. 4-Dienlorobenzene One iMtajon) 2. Nitration 1 1 a Sy __uno, No. \D aacse> + 1-Chlore-2-nitrobenvene iwinon No. Lechter on 3. Sulphonation é a ‘ \ nso. SO.H ~ b= de 2-Chlorobenzene sulonic acid SoH (Minor) 4-Chirobensene milfonicinctd (iajon 4. Friedel-Crafts: i ‘ 5 ic ie aaa Cis Ss Alkylation reaction () cencr enes (J 1-Chloro-2-methylbenzenc cH, (snon) 1-Chloro-4-methylbenzene istajon 4, Friedel-Crafts : C9 ¢ Acetylation reaction Anny AIC, cyte . QO 2-Chioroacetophinone gf (iain) chy en Major) IV. Elimination reactions Saytzeff rule “in dehydrohalogenation reactions, the preferred product is that alkene which has the greater number of alkyl groups attached to the doubly bonded carbon atoms.” CHsCH,CHBrCH; "> CHsCH;CH=CH; (19%)+ CHyCH=CHCH; (81%) V. Reaction with metals. 1. with Mg-Grignard reagents. CHsCH,Br + Mg—"_> CH3CH;MgBr It’s known as organo-metallic compounds. ‘The carbon-magnesium bond is covalent but highly polar, with carbon pulling electrons from 237Enrichment XIl CBSE CHEMISTRY electropositive magnesium; the magnesium halogen bond is essentially ionic. Grignard reagents are highly reactive and react with any source of proton to give hydrocarbons. E.g. Water, alcohols, amines, (CH3CH2MgBr +H20° ighly reactive with water to give hydrocarbons therefore necessary to avoid even traces of Itis > CHsCHs + MgBr(OH) moisture from a Grignard reagent. On the other hand, this could be considered as one of the methods for converting halides to hydrocarbons. 2. With Na AlkyV/aryl halides react with sodium in dry ether to give hydrocarbons containing double the number of carbon atoms present in the halide. a, Wurtz reaction - for haloalkane. CH3CH,Br + 2Na+ CH3CH2Br Pont (CHsCH; CH3CH + 2NaBr b. Wurtz- Fitting reaction- for haloarenes with haloarenes. aye ¢. Fitting reaction- for haloarenes siy emer Compounds Uses [Harmful effect Dichlormetha Solvent as a paint remover, as a ne (Methylene | propellant in aerosols, and as a process Harms the human central nervous system. Exposure to lower levels of methylene chloride) solvent in the manufacture of drug sand | chloride in air can lead to slightly impaired a metal cleaning & finishing solvent. | hearing and vision. Higher levels of methylene chloride in air cause dizziness, nausea, tingling and numbness in the fingers and toes. In humans, direct skin contact with methylene chloride causes intense burning and mild redness of the skin, Direct contact with the eves can burn the cornea. Trichloro- | Refrigerant R-22. It was once used as a_| Inhaling chloroform vapours depresses the methane general anaesthetic in surgery but not | central nervous system, damage to the liver (Chloroform) | now. Chloroform is slowly oxidised by | (where chloroform is metabolised to air in the presence of light to an phosgene) and to the kidneys, and some extremely poisonous gas, carbonyl people develop sores when the skin is chloride, also known as phosgene. It is_| immersed in chloroform. therefore stored in closed dark coloured bottles completely filled so that air is kept out, 2CHCIs+07>2COCl+2HCI Triiodo- Tt was used earlier as an antiseptic The antiseptic properties are due to the methane liberation of free iodine and not due to odoform) iodoform itself. 238Enrichment XIl CBSE CHEMISTRY Tetrachloro- | Refiigerents and propellants in aerosol _| The most common effects are dizziness, methane cans. It was also used as a cleaning light headedness, nausea and vomiting, (Carbon fluid both in industry, as a degreasing | which can cause permanent damage to nerve tetra- agent and in the home as a spot remover | cells. When carbon tetrachloride is released chloride) and as a fire extinguisher. into the air, itrises to the atmosphere and depletes the ozone layer. There is some evidence that exposure to carbon tetrachloride causes liver cancer in humans. Freons They are extremely stable, unreactive, | It diffuses unchanged into the stratosphere. (Tetra chloro methane) by non-toxic, non-corrosive and easily liquefiable gases. Freon 12 (CCF is In stratosphere, freon is able to initiate radical chain reactions that can upset the Swarts usually produced for aerosol natural ozone balance. reaction propellants, refrigeration and air conditioning purposes. PP -Dichlo- | DDT, the first chlorinated organic The chemical stability of DDT and its fat rodipheny insecticides. It was effective against the | solubility compounded the problem. DDT is trichloro- mosquito that spread malaria. But not metabolised very rapidly by animals; ethane(DDT _| later, many species of insects developed | instead, it is deposited and stored in the fatty resistance to DDT tissues. If ingestion continues at a steady £ rate, DDT builds up within the animal over time. It has a high toxicity towards fish. (CERT EXAMPLES 10.1 Draw the structures of all eight structural isomers that have the molecular formula CsHyBr. Name each isomer according to IUPAC system and classify them as primary, secondary or tertiary bromide. Ans. cH,-CH, -CH, -CH, -CH,Br 0 (9), tromopentane () Primary ) cH, I Gin CHC, -CH-CHBr Bromo 2ethylbsane Primary ) ar | CH, -CH, -CH-CH, CH, 2romopentane Secondary) cH, wii) | CH, -C-CH, -CH, | Br 239 2-Bromo-2-methyloutane (Tertiary (iit) cH, w | CH, -CH-CH, -CH,Br 1. Bromo-dmehylbutane Friary thi, I cH, -C-CH,Br w ; oe cn, 1. iomo2dimethypropane Fmary cH, Br 1d CH, -CH-CH-cH, 2Bromo-Smethylbutane Gecondary Br CH, ~CH, CH, ~CH-CH, 2.romopentane (Secondary)Enrichment XIl CBSE CHEMISTRY 10.2 Write IUPAC names of the followin, HC HC cH, oe wi —_— (iii) H HC H, Hc (i) HC on _— H hl Br u Ans. (i) 4-Bromopent ene (io $romo2 mayb ene (iti) 4-Bromo-3-methylpent-2-ene (i) 1-Bromo-2-methylbut-2-ene (v) 1-Bromobut-2-ene (vi) 3-Bromo-2-methylpropene 10.3. Identify all the possible monochloro structural isomers expected to be formed on free radical monochlorination of (CH;);CHCH;CHs. Ans.) Cii,-CH-CH, -CH,CI @ ——cu,-cH-cu-cuy, I robo? cH, cn, Leiorodmetybuane cl i) I () ¢ CH, -C-CH, - CH, ) on. 1-chiow-2metyt bane 2chloro-2methyl butane 10.4 Write the products of the following reactions: @ H + HBr —> H Hl i CH, —CH, —CH=CH, + HCl —> CH, ~C=CH, + HBr Bast (iii) | AMR. oe « | Ans. (i) CH= CHL, cH-c ce ‘pay tn ese Se) tron he w a CH, -CH, ~CH=CH, HCI". CH, - CH, -CH-CH, Butene 2.Chlorobutane 240Enrichment XIl CBSE CHEMISTRY 10.5 Ans. 10.6 Ans. 10.7 Ans. Gi phenyl prope {ally benzene) omo-Spheny! propane Haloalkanes react with KCN to from alkyl cyanides as main product while AgCN form isocyanides as the chief product. Explain, KCN is an ionic compound and provides cyanide ions in solution, Although both carbon and nitrogen atoms are in a position to donate electron pairs, the attack takes place mainly through carbon atom and not through nitrogen atom since C—C bond is more stable than C—N bond. However, AgCN is mainly covalent in nature and nitrogen is free to donate electron pair forming isocyanide as the main product, because nitrogen has more electron density than carbon. In the following pairs of halogen compounds which would undergoing S,2 reaction faster ? @ “Ny and XX wo Cana ‘Shows faster SN? reaction because it is primary halide. G_A_A _, Asiodineis attr teving etoap because ofits are of its large size, it wil 1. be released at a faster rate in the presence of incoming nucleophile, a Predict the order of reactivity of the following compounds in Sx1 and Sx2 reactions. (@) The four isomeric bromobutanes : (b) C,H,CH,Br, C,H,CH(C,H,)Br, C,H,CH(CH,)Br, .C(CH, (CH, Br. (a) We know the order or reactivity of alkyl halide towards Sx1 and Sy2 reactions as follows. For Sst Tertiary halide > secondary halide > Primary halide > methyl halide For S32 ‘Methyl halide > Primary halide > Secondary halide > Tertiary halide Reactivity in Sy1 (CHCH,CH,CHBr < (CH) CHCH,Br < CHsCH;CH(B1)CHs < (CH3);CBr of the two primary bromides, the carbocation intermediate derived from (CH,):CHCHpBr is more stable than derived from CH,CH,CH;CHBr because of greater electron donating inductive effect of (CHs),CH— group. Therefore, (CHs),CHCH,Br is more reactive than CHsCH,CH:CHBr in Syl reactions. CHsCH,CH(Br)CHs is a secondary bromide and (CH);CBr is a tertiary bromide, Hence, the above order is Sxl Reactivity in $x2 CHCH,CH;CHyBr > (CH;)xCHCHBr > CH\CHsCH(B1)CH; > (CH,),CBr The reactivity in Sy2 reactions follows the reverse order as the steric hinderance around the electrophilic carbon increases in that order. (b) Reactivity in Sxl 241Enrichment XIl CBSE CHEMISTRY 10.8 Ans. 10.9 Ans. 10.1 Ans. (C6HsC(CHs)(CcHe)Br > CoHsCH(CeH)Br > CsHyCH(CH5)Br > CeHsCH2Br of the two secondary bromides, the carbocation intermediate obtained from CsHsCH(CiHs)Br is more stable than obtained from C.HsCH(CH,)Br, because it is stabilized by two phenyl groups due to resonance Therefore, the former bromide is more reactive than the latter in Sy1 reactions. Reactivity in $y2 Phenyl group is bulkier than a methyl group. Therefore, CeHsCH(C¢Hl.)Br is less reactive than C(HCH(CHs)Br in Sy2 reactions. So, CaHsC(CH3)(CoH)Br < CeHsCH(Clls)Br < CeHCH(CHs)Br < CoH,CHBr. Identify chiral and achiral molecules in each of the following pair of compounds. Br CH,CH,CH,CH,Br The objects which are non-superimposable on their mirror image (like a pair of hands) are said to chiral and this property is known as chirality. While the oy H objects are superimposable on theit = mirror image ate called ‘CH,CHCH,CH, qua achiral. Although chlorine is an electron-withdrawing group, yet it is ortho-, para-directing in electrophilic aromatic substituting reactions. Why ? Chlorine withdraws electrons through inductive effect and releases electrons through resonance. Through inductive effect, chlorine destabilizes the intermediate carbocation formed during the electrophilic substitution. ‘Through resonance, halogen tends to stabilize the carbocation and the effect is more pronounced at ortho- and para-positions. The inductive effect is stronger than resonance and causes net electron withdrawal and thus causes net deactivation, The resonance effect tends to oppose the inductive effect for the attack at ortho- and para-positions and hence makes the deactivation less for ortho- and para- attack. Reactivity is thus controlled by the stronger inductive effect and orientation is controlled by resonance effect. ‘Write the structures of the following compounds : (@. 2-Chloro-3-methylpentane (ii) 1-Chloro-4-ethyleyclohexane (ii) 4-tert-Butyl-3-iodoheptane (iv) 1, 4_Dibromo-but-2-ene () 1-Bromo-4sec-butyl-2-methylbenzene, 242Enrichment XIl CBSE CHEMISTRY 10.2 Ans, 10.3 Ans. co) 10.4 Ans. 1 CH, ~CH-CH-CH,-CH, cl CH, 2-Chloro-3.methylpentane Why is sulphuric acid not used during the reactions of alcohols with KI? 1;S0, is an oxidizing agent. It oxidizes III produced during the reaction to Iz 2KI+H,SO, —> 2KHSO, +2HI 2HI+H,SO, —> H,0+1, +S0, ‘And thus prevents the reaction between an alcohol and HI to form an alkyl iodide, so a non-oxidising acid such as HyPO« is used in place of H:SO«. CH,CH,OH +KI+H,P0, + CH,CH, + KH,PO, +H,0 Write structure of differ ent diahlogen|detivatives of propiine. © — BrCH,>CH,-CH,Br wo pee, Br (iii) aud Br-CH-CH-CH, 1, 2-Dibromopropane Br Lo CH,-@-CH, 1, 1-Dibromopropane Br Br 2 Among the isomeric alkanes of molecular formula C;H,;. Identify that on photochemical chlorination yields. i) a Single monochloride ii) Three monochloride iii) 2-Dibromopropan urmonochloride () All the H atoms are equivalent. Therefore, replacement of any one of them will give the same product. en, cH, I cH, -¢-cn, cH,-c-cH,-c! on, i cH, Neopentane. (ii) There are three groups of equivalent hydrogens designated as 1, 2 and 3. This replacement of any 243Enrichment XIl CBSE CHEMISTRY one of the equivalent hydrogens will give the same product. Therefore, three isomeric monochlorides are possible. CH,-CH, ~CH, CH, CH, ~CH, -CH,-CH.CL CH, CH—CH, cH, cl, -ci-cn, -cH, a a } (a) (a) (iii) There are four types of equivalent hydrogens designed as 1, 2,3 and 4. Therefore, four isomeric monochlorides are possible. 1 2 4 CH, -CH-CH,—CH, For example : cH, cl | CI-CH, -CH-CH, -CH,, CH, ~C-CH, CH, I cH, CH, () (i) CH, ~CH-CH-CH,, CH, ~GH-CH, -CH,-Cl CH, Cl CH, (mm) (Iv) 10.5 Draw the structure of major monohalo product in each of the following reacti OH 6 .CH,CH3 @ (6) ) Br, , Heat, or ~ SOC, —> [om wie N cH,OH cH. © 2 @ . + HCL —> +m > HO (© CH,-CH,Br+Nal —> 0 we +B SE 244Enrichment XIl CBSE CHEMISTRY Ans, 10.6 Ans. OH @ cl Cyclohexand Chiorocyclohexane Br CHyCHy bac, () Sor er Sr on zy A 4 Nitosthybenzene 1-Brome-+.(4-iropheny)ethane © ow J Ho 46 {stydonyntnipene ‘chironatipnen CHy CH, d) @ Cr +H ttre CK ‘atyopschore ‘Hose: nthytoane () CH, -CH,Br +Nal 43 GH) =CH,1-+)NaBr er 0 O + By, Bes Be Cydcherone 8rompjckhaere Arrange each set of compounds in order of increasing boiling points. (@ Bromomethane, bromoform, chloromethane, dibromomethane. (6) 1-Chloropropane, isopropyl chloride, I-chlorobutane. We know that boiling point is directly proportional to the size of halogen with same alkyl group or ‘compound directly proportional to the molecular mass. ‘The boiling points increase as the number of halogen atoms increases. Combining all the arguments presented above, the boiling points of the four ‘compounds discussed above increases in the order Chloromethane < bromomethane Secondary > Primary > Methyl @ Gl 3° alkyl halide react faster than 2° alkyl halide due to greater stability of 3° carbocation. a (ii) AAYX> 2° alkyl halide react faster than 1° alkyl halide. 246Enrichment XIl CBSE CHEMISTRY 10.9 Ans, 10.1 Identity A,B, C, D, E, R and R' in the following: C= breve 2205 4 5 R-Br+ Mg 2" C —%° 5 CH,-CH-CH, | D CHy CH Hy ch, MAS RIX) D ESSE Cy Oy otimot Croton Magnan cpttman 0) R-B+Mg —“® 5 RMgBr —@° 5 CH,-CH-CH, ‘Ay: I “or D Since D gets attached to same C-atom on which MgX or X was present so that Br | I R-Br= CH,-CH-CH, or = R= CH,-CH-CH, — and ie So CH, — CH= MgBr cues, I cH, -€-c-cH, 2st propane (6) L Na / ether Note : Tert-alkyl halides do not undergo Wurtz reaction. Therefore, the question is not correct, NCERT EXERCISES Name the following halides according to IUPAC system and classify them as alkyl, allyl, benzyl (primary, secondary, tertiary), vinyl or aryl halides: @ (CHs),CHCH(C)CHs Gi) CHCH;,CH(CH,)CH(CH,)C1 (iif) CHyCH,C(CH,):CH1 (is) (CHy);CCH;CH(Br)CHs () CH,CH(CH,)CH@NCH; (vi) CHsC(C:Hs),CHBr 247Enrichment XIl CBSE CHEMISTRY (ii) CHyC(CD(C2H.)CH:CH, (x) CH,CH = CHC(Br\(CHs)s (i) m-CLCH,C,.H,CH,C(CH,); (viii) CH,CH = C(C)CH;CH(CH,) (x) p-Cl-CH-CH(CH)2 (xii) o-Br-CgH,CH(CH3)CH,CHs. Ans. ea Ss kk @ CH,-CH-CH-CH, @ — CN,-Cu,-Cu-Cn-E.n1, | || CH, Cl CH, Cl 2.cherod-etryutane 2:Chor--atnyherane ‘gina (eocondoy) ‘A Ral ecco) CH, CH, Wid ' a CH,~CH, ~C-CH,-1 - cH, -CH= by CH, Br ‘ode 22 inathyutane m0, 3-dmetnyt-phenbvtane ‘yal Pena) res Sonzvic hte (Secon) so: cat, ) CH, -CH-CH-CH, i ji ” i wi) cH,-¢-¢H, -Br CH, Br bn, 2.Bromo,-dnty.tne tem tamiznennaee ‘Agha (Seconda) pay (i) a Gu,-Cu= ¢-Cn,-Cu-Cu, | ca CH, 2.GhlreS.rtto2-one nate -Chlrod-matypntane 23 (i), Alte odiaryy = @ Pa a CH,-CH- C-C-CH, a—¢ Yu, CH-CH, | Cl Br |-Chlero(2methyprop benzene 48:04 mein pert2-on8 ‘Aina ‘av ha orton) cH Br wo ‘yb tutu, -¢ CH,-¢-CHy (xn aa H,-CH, CI CH, cn,¢ cH, : {-Bromo-2tetrypropy benzene 41-Chloromethy-3-(2, 2-dimethyipropy)) benzene Anh nelte ‘Bonzyl hte fray) 10.2 Give the IUPAC name of the following compounds : (@ CH\CH(C)CH(Br)CH; Gi CICH,C= CCH,Br (@) CHyC(@-CIC.H):CH@r)CH; (i) CHF,CBrclF (i) (CCh),CCI (vi (CH),C-CH = CYC Hap 248Enrichment XIl CBSE CHEMISTRY Ans. © On,-CH-Cn-Cu, i) I a Br 1-Bromo-t-hlrabutane i) CI-CH, -CC-CH, -Br Ww) al Br (vy) CH,-C-CH-CH, wp cl 2-8rome-3, is (-eheropheny!) butane 10.3 Give the IUPAC name of the following compounds? ( 2-Chloro-3-methylpentane (iii) 1-Chloro-4-ethyleyclohexane (0) Perfluorobenzene (vii) 1-Bromo-4-sec-butyl-2-methylbenzene (iif 1, 4-Dibromobut-2-ene. Ans. 0 CH, -CH-CH-CH, - @ I cl cH, ww pF 0 oa F F FoF Br Q CH, (ii) ir (vill) Is H,C-CH-CH, ~CH, 249 ¢ F CH fbr FF 1-Bromo-t-chloro-,2,2-iftuoroethane 4.4, 1,2,3,3, SHopachioro2- 6,4, ‘thloremathylpropane) cH, 4 12 CH, ¢ ou eX V1 cH, Cl 1-Chlorot-4odopheny)-3, S-dimethybbut-one G) p-Broniochlorobenzene (iv) 2-(2-Chlorophenyl)-I-iodoctane (vi) 4-tert- Butyl-3-iodoheptance a CH bn tntnn CH, CH, CH, CH,-1 CH, -CH-CH-CH, | CH, 5 CH,-CH,Enrichment XIl CBSE CHEMISTRY 10.4 Which one of the following has the highest dipole moment ? (@) CHLCh () CHC (© CHCL, @ CCh Ans. The dipole moment of CCI, is zeto because symmetrical. In CH,Cl, the resultant of two C—Cl dipole ‘moment is reinforced by the resultant of two C—IT. While in CHCl; the resultant of two C—Cl dipoles is opposed by the result of CH and C—Cl bonds. As result, the dipole moment of CHCl; smaller than CHCl, because the bond dipole of third C—Cl bond opposes the resultant of bond dipoles of the other ~Clbonds. Therefore, CHCl has the highest aie moment. NZ. NZ. NZ “NM 2N, ZN. 105 A hydrocarbon CsHye does not react with chlorine in dark but gives a single monochloro compound C;H,Cl in bright sunlight. Identify the hydrocarbon. ‘Ans. Since the hydrocarbon gives only one monochloro compound, it indicates that all the hydrogen atoms in the hydrocarbon are equivalent, Thus, the compound is eyclopentane. Ova o> Suniigie Gyctopentane 10.6 Write the molecular formula CHsBr. ‘Ans, For the molecular formula C4119Br four isomers are possible : isomers of compound having (CH, CH, ~CH, ~CH,Br ®)_ oH.=-cH-cH,-cH, Br CH, -CH-CH,Br 2Peomobutane | CH, cH, | CH, -C-CH, 1-Bromo-2-methylpropane 1 10.7 Write equations for the preparation of I-iodobutane from Br (@ Butan-1-o1 (i) 1-Chlorobutane 2-Bromo2-methylpropane (i) Bute Lene, Ans. () CH,CH,CH,CH,OH + HI —> CH,CH,CH,CH,I+H,0 (ii) CH,CH,C H,C1+Nal —“8*> CH,CH,CH,CH,I+ NaCl (Finkelstein reaction) () — CH,CH,CH=CH, + HBr —™* 5 CH,CH,CH,CH,Br (Anti Markonikov rule) CH,CH,CH,CH,Br+ Nal > CH,CE H,CH,I + NaBr (Finkelstein reaction) 250Enrichment XIl CBSE CHEMISTRY 108 ‘Ans, 10.9 Ans. 10.10 Ans. 10.11 ‘Ans. ‘What are ambident nucleophiles ? Explain with an example. Those groups which can attack nucleophilic centre from two sites are called ambident nucleophiles, For =NC™ and —NO},-ONO™. The example: —C! ¢ nucleophiles can attack from either of these sites depending upon the reaction conditions and the reagent used. CH,CH,CI + KCN —> CH,CH,CN + KCI CH,CH,CI + AgCN —> CH,CH,NC + AgCl ‘Which compound in each of the following pairs will react faster in Sy’ reaction with OH”? (a) CHsBr or CHE (8) (CHy)sCCI or CHSC (a) CH, will react faster because C—T bond undergoes cleavage more easily as compared to C—Br bond. (b) CHCl will react faster because in it the carbon carrying halogen is sterically less hindered, Predict all the alkenes that would be formed by dehydrohalogenation of the following halides with sodium ethoxide in ethanol and identify the major alkene : (@ —1-Bromo-1-methyleyclohexane (i) 2-Chloro-2-methylbutane (iil) 2,2,3-Trimethyl-3-bromopentane. Br CH, w - Cio CH, HBr 1-bromo-Lmethy! 1LMethycyelohexene “ytlohoane ‘tae w oe oh CH,-C-CH,CH, —St0#GILON CH —C=CHCH, 2-Methylbut2ene a (oon) 2.chlor-2-methy] butane Gi cH GAs CH, - ¢ —C-CH,CH, —S#2MSH0" 5 CH, -C-C=CH-CH, CH,CH, CH,CH, 2,2 Simetbyi-bromopentane 5,4 4:Trimthyl pent 2-ene ‘ataes) How will you bring about the following conversions ? Ethanol to but-L-yne (i) Ethane to bromoethene Propene to I-nitropropane (jv) Toluene to benzyl alcohol Propene to propyne (0) Ethanol to ethyl fluoride Bromomethane to propanone (viii) _But-L-ene to but-2-ene I-chlorobutane to octane (x) Benzene to biphenyl. (@ CH,CH,OH —> CH,CH,CL —“*+> CH,CH,C = CH +NaCl 251Enrichment XIl CBSE CHEMISTRY 10.12 Ans. (i) CH,—CH, + Br, S85 CH,CH,Br 8“, CH, = CH, +Br, CH, -Br — | +2KOH (Ale) gq» CH= CH+HBr —> CH,-CHBr CH, -Br a8 ne Sromodhne (iii) CH,CH = CH, + HBr 35> CH,CH,CH,Br —*S-> CH,CH,CH, NO, We) On, cl, —Sut O- cH,ci 2382 O- cHOH Toluene Berwylehioride Benzyl alcohol () CH,CH=CH, +Br, —> CHACH—CH, was, CH,C = CH aa Br Br 1.2 ditnomnopropane wi) OH + CH,CH,Br — > CHCH,F cH, (vii) low CH,Br + KCN, CH,CN + CH,MgBr —> CH,-C2N !MgBr nein Monroe _ Met mag oh OH Hsieh, CH, —C-0 + NH, +Mg—Br (1) CH.CH,CH=CH, —! > CH,CH,CHCH, —*©"5 CH,CH=CHCH, ele ie Bade Br (0) 2s CH,CH,CH,CH,Cl —***_> CH,CH,CH,CH,CH,CH,CH,CH, ® ee * ter Benzene Chiorobenzene Biphenyl Explain why : (The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride. (ii) Alkyl halides, though polar, are immiscible with water. (ii) Grignard reagents should be prepared under anhydrous conditions, ( In Chlorobenzene CCl aquires double bond character due to resonance effect. While in C-Cl bond in cyclohexyl chloride is a single bond. We Know also the double bond between C and CL 252Enrichment XIl CBSE CHEMISTRY 10.13, Ans. 10.14 Ans. has shorter bond length than single bond between C and Cl. As dipole moment is a product of charge and distance, So chlorobenzene has lower dipole moment than cyclohexyl chloride due to Tower magnitude of —ve charge on the CI shorter C—C1 bond length. (i) Alkyl halides eannot form hydrogen bonds with water molecules and hence are insoluble in water. (iii) Grignard reagents react with water and get decomposed to produce alkane RMgX # 10 —> R-H | MgX(OH) Hence, they have to be prepared under anhydrous conditions, Give the uses of Freon-12, DDT, carbon tetrachloride and iodoform. See notes ‘Write the structure of the major organic product in each of the following re () CH,CH,CH,C1+ Nal "> (i) (CH,)sCBr + KOH —S> (iii) CH\CH(Br) CH,CH, + NaOH ==> (iv) CH,CH,Br + KCN —5 (9) C,H,ONa + HSC —> (vi) CHCH,CH,OH + SOC, —> (vii) CH;CH,CH+CH, + HBr —="* > (iit) CHSCH = (CH); + HBr —> @ — CH,CH,CH,CI | Nal *> CH,CH,CH,I + NaCl cH, @) (cH), -CBr+ KOH 24+ CH, -C=CH, + KBr+H,0 Br OH I I CH, -CH-CH, -CH, +NaOH “4 CH,-CH-CH,-CH, +NaBr+H,0 (ii) 2 BROMOBUTANE Buse! (vy) CH,-CH,Br + KCN 2! CH, -CH,CN + KBr () —C,H,ONa + C,H,Cl —> C,H,-O-C,H, +NaCl (i) CH,-CH,~CH,OH + SOCl, —> CH,CH,CH,CI + SO, + HCI (ii) CH, -CH, —CH=CH, + HBr ““* 4 CH, -CH, -CH, -CH,Br CH, CH, I I (i) CH, -CH-C-CH, + HBr —> CH,-CH, -C-CH, 2st | Br onan 253Enrichment XIl CBSE CHEMISTRY 10.15 Ans, 10.16 Ans, 10.17 Ans. 10.18 Ans, 10.19 Write the mechanism of the following reactio nBuBr + KCN —2%%°_5 nBuCN tut This is a nucleophilic substitution reaction. Since the alkyl halide is 1° and the nucleophile (CN~) is a strong nucleophile, the reaction is likely to take place through Sy? mechanism. Arrange the compounds of each set in order of reactivity towards Sy? displacement : (@ 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane (ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 3-Bromo-2-methylbutane (i) 1-Bromobutane, 1-Bromo-2, 2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-3-methylbutane. In Sy’ displacement the order of reactivity of various types of alkyl halides is Primary > Secondary > Tertiary (I°>2°>3°) For alkyl halides of the same class the one which sterically less hindered is more reactive. i.l-Bromopentane > 2-Bromopentane > 2-Bromo-2-methylbutane ii, 1-Bromo-3-methylbutane > 3-Bromo-2-methylbutane 2-Bromo-2- methylbutane iii, 1-Bromobutane > 1-Bromo-3-methylbutane > 1-Bromo-2-methylbutane > 1-Bromo-2, 2+ dimethyl propane. All these halides are 1°. ‘The halide which has less steric hinderance about the carbon to which halogen atom is attached, is more reactive towards Ss” displacement. (Out of C,HsCH;Cl and CoH CH,CH,CH,Br — > CH,CH,CH,OH (i) CH,CH,OH —“*5 CH,CH,cl “8&5 CH,CH,C=CH (i) CH,CH,CH,Br #8), CH,CH=CH —#5 CH,CHCH, Br a) On, =>> (crc aust, (\—cH,on wy Toluene ‘Benzyl chloride ‘Benzyl aleobol wo) @- cx,04 see -cna (cn > ©-éu, b00H (vii) CH,CH,OH "5 CH,CH,Br "5 CH,CH, 2 htenie it itd) \—™, enue O-ncr ey «a OCH, CH, lod (s) 2CH,CH.CHCH, jetzt CHCH,CH-CHCH,CH, cl 2tabune \40imeee (7 CH, (xi) CH,CH,Cl “4 CH,CH,CN —®°"4 CH,CH,COOH Citas Propose Fron 255Enrichment XIl CBSE CHEMISTRY 10.20 Ans. 10.21 ‘Ans. (xi) CH,CH,CH= CH, —2%> CH,CH,CH,CH,Br —-» CH,CH,CH,CH,I (sili) CHYCHCH, —=*4 CH,CH= CH, —SSi=h 5 CH,CH,CH,OH t, Poor ot &v) CH, ~CH-cH, th cenwotl_ CHI, + CH,COONa + Nal + 5 H,0 20H a on @) co. HNO, + cans H,S04 —omouensia , 7) Si io K tere wb, wb, oo) CH,CHCH, —ekol_, CH,CH=CH, —-> CH,CH,CH,Br 1 noe emcees (evil) 2CH,CH,Cl — 28> CH,CH,CH,CH, (xvili) O20, ore a Neate ewere Trinh Dem ca, iH, GH oe) CH, -C-CH, 808 CH,-C=CH, —-> CH,CHCH,Br I Tee tenon 2s pope Daya (ex) + CHCl, + 3KOH —> + 3KC1 + 31,0 anit ionoen Pinos ‘The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in presence of alcoholic KOH alkenes are major products. Explain. ‘When an alkyl halide is treated with some nucleophile, there is always competition between substitution and elimination to take place. In the present case, substitution would result in alcohol as product whereas elimination would result in alkene as product. In the presence of solvent of low polarity such as alcohol, climination reaction is favoured whereas in the presence of solvent of high polarity (such as water) substitution is favoured. Primary alkyl halide (A) C,HsBr reacted with alcoholic KOH to give competition (B). Compound (B) is reacted with HBr to give (C) which is an isomer. When (A) was reacted with sodium metal it gave a compound (D) CyHys with is different from the compound formed when n-butyl bromide, is reacted with sodium, Give the structural formula of (A) and write the equation all the reactions. For C.HsBr, two primary halides are possible CHsCHsCH:CH:Br (n-butyl bromide) and (CHs),CHCH,Br (iso-butyl bromide), Since (A) is not n-butylbromiide, it iso-butyl bromide, 256Enrichment XIl CBSE CHEMISTRY Thus, (A) is cH, Br os CH CH, ~CH-CH, ~Br+ KOH (ale.) ——» CH, -C= CH, +KBr+H,0 (A) (B) CH, cH, CH,-C=CH, + HBr —#_> CH. é -CH, be © CH, CH, CH, . | 2CH, -CH-CH,Br + 2Na — > CH, -CH-CH, - CH, -CH-CH, 2. iayeoe Gs (P) 10.22, What happens when (@ — m-Butyl chloride is treated with alcoholic KOH. (ii) Bromobenzene is treated with Mg in tlie presence of dry ether. (iii) Chlorobenzene is subjected to hydrolysis: (jv) Ethyl chloride is treated with aqueous KOH. (») Methyl bromide is treated with sodium in the presence of dry ether. (vi) Methyl chloride is treated with KCN ? Ans. () n-Butyl chloride undergoes f -elimination to yield but-1-ene. CH,CH,CH,CH,Cl —“*"» CH,CH,CH=CH, + KCI +H,0 (ii) Grignard reagent is formed Oi ve te, as bromotenvee tery grein rome © (\—a + awa E> (\— ONa + NaCl +H,0 cae Seep iv) It undergoes nucleophilic substitution to yield ethyl alcohol CH,CH,Cl + KOH (aq) —> CH,CH,OH + KCI v)Methylbromide undergoes Wurtz reaction to yield ethane. 2 CH,Br + 2Na —8* 5 CH,-CH, + 2NaBrEnrichment XII CBSE CHEMISTRY vi)Methyl cyanide is formed by nucleophilic substitution. CH,Cl_ + KCN —>+ CH,CN + KCI 258Enrichment XIl CBSE CHEMISTRY 11. Alcohols, Phenols and Ethers An alcohol contains one or more hydroxyl (OH) group(s) directly attached to carbon atom(s), of an aliphatic system (CHsOH) while a phenol contains OH group(s) directly attached to carbon Classification: 1, Monobydric aleohols: They contain only one hydroxyl group in HgC—CH,-CH,OH their structures. Primary: OH group attached carbon contains one alkyl group. HgC—CH,-CH,OH Secondary: OU group attached carbon contains two alkyl groups. HyC-HC——CHg OH Tertiary: OH group attached carbon contains three alkyl groups. HaG HagoC—6—cH, 6H 2. Dihydric alcohols: They contain two hydroxyl group in their CI—CHyCH)-CH,OH structures Germinal: Two OH group are present on the same carbon atom, 9H Hé—cH, ou Vicinal: Two OH group are present on the adjacent carbon atom. HeS—GH2 OH HO 3. Trihydric alcohols: HO—CH,CH—CH,0H They contain three OH group in their structures. OH On the Basis of sp’ of hybridisation Vinylic alcohols: These are the compounds in.whieh-the OH¢graup is H»C—=CH-OH bonded to a sp2-hybridised carbon atom of a carbon-carbon double bond(C = C) Aryl alcohols: These are the compounds in which the OH group is ee bonded to the sp2-hybridised carbon atom of an aromatic ring He *SeH nd gin Allylic alcohols: These are the compounds in which the OH group is. HgC===CH-CH,~OH bonded to an sp3-hybridised carbon atom next to carbon-carbon double bond (C=C) Benzylic alcohols: These are the compounds in which the OH group gion is bonded to a sp3-hybridised carbon atom next to an aromatic ring. = H¢~ “ScH He gen IUPAC: Alkanol and Common name: Alkyl aleohol OH cn, cH, CH, Ho~ Fert ‘OH | on on Propane -1, 2, 3-triol _Cyclohexanol 2-Methyleyclopentanol Preparation of Aleohols List of preparation () From alkenes ‘By acid catalysed hydration - Markovnikov’s rule 259Enrichment XIl CBSE CHEMISTRY * By hydroboration —oxidation- opposite to Markovnikov’s rule. (i) From carbonyl compounds by reduction Aldehydes - (catalytic hydrogenation/reducing agent) -1" Alcohols ‘© Ketones- (catalytic hydrogenation/reducing agent) -2° Alcohols * Carboxylic acids - (reducing agent) -1° Alcohols + Esters- (catalytic hydrogenation) -1° Alcohols ii) Grignard reagents with * Formaldehydes (methanol) -1° Alcohols © Other aldehydes-2" Alcohols + Ketones-3” Alcohols Preparation reaction i, From alkenes a. By acid catalysed hydration CH;CH=CH, + H,0—"_, CH,CHOHCH Mechanism: Step 1: Protonation of alkene to form carbocation by electrophilic attack of H30+ 120 +H" > HO" +. By hydroboration ~oxidation: CH,-CH-cH, + G1-BM),——> cH-on (CH,-CH.-CH).B 1,0,, OF 8CH,-CH,-CH,-OH + B(OrD, r The addition of borane to the double bond takes place in such a manner that the boron atom gets attached to the sp? carbon carrying greater number of hydrogen atoms. The alcohol formed by the addition of water to the alkene in a way opposite to the Markovnikov’s rule. In this reaction, alcohol is obtained in excellent yield. ii, From carbonyl compounds 1. Aldehydes - (catalytic hydrogenation/reducing agent) -1° Alcohols rcno th , R-CH,OH 2. Ketones- (catalytic hydrogenation/reducing agent) -2° Alcohols , Pav R-CO-R’ ——2-> RCHOHR’ 260Enrichment XIl CBSE CHEMISTRY 3, Carboxylic acids - (reducing agent) -1° Alcohols r-coon HAI, R-CILOI ‘However, LiAlH4 is an expensive reagent, and therefore, used for preparing special chemicals only. Commercially, acids are reduced to alcohols by converting them to the esters, followed by their reduction using hydrogen in the presence of catalyst (catalytic hydrogenation) 4, Esters- (catalytic hydrogenation/ LiAIH4) -1" Alcohols R-coor’ HAN, R-CH;OH + R’-OH iii. Grignard reagents The first step of the reaction is the nucleophilic addition of Grignard reagent to the carbonyl group to form an adduct. Hydrolysis of the adduct yields an alcohol. ‘64 - ~c-6 Me HO, >C— OH + Mg(OH)X ne fos Ppoiex] BA pron + sao f a Adduct a. Formaldehydes (methanol) give 1° Alcohols: HCHO + RMgX > RCH,OMgx 2, RCH,OH + Mg(OH)X b. Other aldehydes give 2° Alcohols. R R , HO | Ho, | | RCHO + RMgX —> RCH omgx —22 R-CH- on + Mg(OH)X c. Ketones give 3” Alcohols. R R 1 x i RCOR + R’MgX ——> R-C-OMgx #2 FOG OH + Mg(OHDX R R Physical Properties: Boiling Points: The boiling points of alcohols increase with increase in the number of carbon atoms (increase in van der Waals forces). The boiling points decrease with increase of branching in carbon chain (because of decrease in van der Waals forces with decrease in surface area). The -OH group in alcohols is involved in intermolecular hydrogen bonding. R Boiling points of alcohols are higher in comparison to ® PO Ho HO" hydrocarbons, ethers, haloalkanes and haloarenes of comparable molecular masses. Boiling point order: Carboxylic acid > Aleohol > Amine > Ketone > Aldehyde > >Ether > Hydrocarbon. Solubility: Solubility of alcohols in water is due to their ability to form hydrogen bonds with water ‘molecules. The solubility decreases with increase in size of alkyV/aryl (hydro phobic) groups. Several of the lower molecular mass alcohols are miscible with water in all proportions. Chemical Properties: Alcohols as nucleophiles: The bond between O-H is broken when alcohols react as nucleophiles. < = R-G—H + TS —> east Protonated alcohols as electrophiles: The bond between C-O is broken when they react as electrophiles 261Enrichment XIl CBSE CHEMISTRY RUCH,-OH + Fi > R-CH,-OH, + HO 1 R R 2 It is based on the cleavage of O-H and C-O bonds, the reactions of alcohols a . Br tag — Br TN Chemical Properti may be divided into two groups. List of reactio LReactions involving cleavage of O-H bond L Reaction with metals: a.Soduim b.Aluminium 2. Esterification-by a.Carboxylic acid b.Acid anhydride c.acetyl chloride. HH Reactions involving cleavage of carbon — oxygen (C-O) bond. 1. Reaction with hydrogen halides: Lucas reagent (conc, HCI and ZnCl) 2. Halogenation: Phosphorus trihalides or SOCl II. Dehydration: a.Inter dehydration b.Intra dehydration IV. Oxidation: a.Mild oxidation b. Strong oxidation c. Catalytic dehydrogenation d.lodoform test. LReactions involving cleavage of O-H bond: 1 Reaction with metals : Alcohols and phenols react with active metals (sodium, potassium and aluminium to yield corresponding alkoxides and hydrogen, a.Soduim: 2R-OH +2Na— 2R-ONa + Hp b Aluminiu em, ocn,-S n+ 2a —e 2(cr- on, 2. Esterification a.Carboxylic acid: ROH + R'-COOH BE R’ SOOR + 1,0 The reaction is carried out in the presence of a small amount of concentrated sulphuric acid. The reaction is reversible, and therefore, water is removed as soon as itis formed. b.Acid anhydride R-OH +(R’-CO),0 (fig) R’-COOR +R’-COOH cAcetyl chloride: R-OH + R’-COC] —**5 R’-COOR + HC] ‘The reaction with acid chloride is carried out in the presence of a base (pyridine) so as to neutralise HCl which is formed during the reaction. It shifts the equilibrium to the right hand side. coon coon on “ ococH, + (cH,co),02 + cH,coon lic acid Acetyisalicylic acid (Aspirin) 262Enrichment XII CBSE CHEMISTRY IL, Reactions involving cleavage of earbon — oxygen (C-O) bond. 1. Lucas reagent: The difference in reactivity of three classes of alcohols with HCI distinguishes them from one another (Lucas test). Alcohols are soluble in Lucas reagent (conc. HCI and ZnCI2) while their halides are immiscible and produce turbidity in solution, In case of tertiary alcohols, turbidity is produced immediately as they form the halides easily. Primary alcohols do not produce turbidity at room temperature. (CH3);C-OH —S#¢ 5 (CHs)3C-Cl+ E20) (CHs),CH-OH #5 (CH3),CH-Cl + H20 CH3CH;-OH —SE#¢ 5 CH3CH2-Cl+ H:0 2, Halogenation: PCls: 3R-OH + PX 3R-X + HsPOs PCs: R-OH + PXs—> R-X + POX; + HX SOCh; R-OH + SOCl— R-X + SO) + HX. II. Dehydration: HO. cn-cu, 443K CH,CH,OH —| 415K ‘aIntra dehydration (with in molecule) ‘Alcohols undergo dehydration to fori alkenes on treating with a protic acid e.g.cone-H280s or H;PO4. ‘b Inter dehydration(between the molecule) When excess of alcohol is heated with con. S03 ‘or H:POy, two molecules condense losing a molecule of water forming ether. OH CH, = CHy+ HO OH 35% HPO, The formation of ether is a nucleophilic CHsCHCHs > CHy- CH = CH: +720 pimatecular reaction (Sx2) involving the attack of cn, cn, alcohol molecule on a protonated alcohol. cri, G-on 2%", oy LH, +40 i 358K CHy Mechanism: Mechanisi Step 1: Formation of protonated alcohol. Step 1: Formation of protonated alcohol HW HH i H-G-G-6-H +l 2 H-G-¢ HA HOH Ethanol Protonated alcohol (Ethyl oxoniam ion) Step 2: Formation of carbocation: It is the slowest step and hence, the rate determining OtH step of the reaction, HHH H-C-C%OHH 2 H- HOW H ¢'+ HO H é H CH,CH,-O-H.+ H’ —> CH,CH-O-H Step 2: Nucleophilic of alcohol molecule attack the protonated alcohol. eH (\ ,-> CH.CH,-O- CH,CH, + H,0 8 Step 3: Formation of ether by elimination of a proton. cucH,-0: cH H 263Enrichment XIl CBSE CHEMISTRY Step 3: Formation of ethene by elimination of a proton, He on H-ch CG = U=C +H bon won HOH Ethene ‘The acid used in step 1 is released in step 3. To drive the equilibrium to the right, ethene is removed as it is formed, — CH,CH,—> CH,CH,-O-CH,CH, + H Elimination Mechanism:Based on stability of carbocations, 3°> 2°> 18 The temperature be kept high . ‘Sx2 Mechanism:Based on the alkyl group should be unhindered, 1°> 2°> 3° The temperature be kept low. TV. Oxidation: a.Mild oxidatior A better reagent for oxidation of primary alcohols to aldehydes in good yield is pyridinium chlorochromate (PCC), a complex of chromium trioxide with pyridine and HCI.CrOsin anhydrous medium is used as the oxidising agent for the isolation of aldehydes. ,OH—Ss_,RCHO RC} Secondary alcohols are oxidised to ketones by chromic anhyride (CrOs) RoR _, RoR ou é Tertiary aleohols do not undergo Mild oxidation reaction due to absence of aeH. b. Strong oxidation: Strong oxidising agents such as acidified potassium permanganate are used for getting carboxylic acids fiom alcohols directly H on Oxidation ° RcHLOH SH, R-¢-0 —>R-C-0 Alehyde Carboxylic Tertiary & Secondary alcohols: Under strong oxidising agents (KMnO,) and elevated temperatures, cleavage of various C-C bonds takes place and a mixture of carboxylic acids containing lesser number of carbon atoms is formed. ¢. Catalytic dehydrogenation: When the vapours of a 1°or 2° alcohol are passed over heated Cu at 573 K, dehydrogenation takes place and an aldehyde or a ketone is formed while 3°alcohols undergo dehydration due to absence of a-H. d.Jodoform test When alcohols containing CHsCHOH- group is treated with iodine and potassium hydroxide, yellow crystals of iodoform and potassium salt of an acid are formed. 264Enrichment XIl CBSE CHEMISTRY TKO cn,01 22 cx,cuo 5 c1,cHo_*2! CHI, + HCOOK LyKoH 1 Kon, CH,CHOHCH, >>. CH,cocn, > cl,cocn, 55. cri,+cH,cooK Phenols: oO 8 & «a, Preparation of Phenols: 1. From haloarenes 2, From benzene or benzenesulphonic acid 3. From Aniline or diazonium salts 4, From cumene(isopropylbenzene) 1.From haloarenes: ci Net ou 2. From benzene or benzene sulphonic acid SoH on 3. From Aniline or diazonium salts: ; nie Ra pa C5 me Cate Coes 4, From cumene (isopropyl benzene): Most of the worldwideproduction of phenol isfrom cumene. oH. pHs Sy at + cH.cocn Physical Properties: In the presence of air, phenols are slowly oxidised to dark coloured mixtures containing quinones. Boiling points of phenols are higher due to the hydroxyl group,which are able to form hydrogen bonding. Solubility of phenols in water is due to their ability to form hydrogen bonds with water molecules. The solubility decreases with increase in size of aryl (hydro phobic) groups. Chemical Properties: 1, Electrophilic aromatic substitutios (@ Nitration 265Enrichment XIl CBSE CHEMISTRY a) With dilute nitric acid at low temperature:—O/P product b) With concentrated nitric acid: -2,4,6. Product. (i) Halogenation: a) Bromine in solvents of low polarity(CHCl: or CS) and at low temperature:—O/P product b) Bromine water:-2,4,6. product . 2. Kolbe’s reaction. 3. Reimer-Tiemann reaction. 4,Reaction of phenol with zinc dust. 5. Oxidation. 1, Electrophilic aromatic substitution: In phenols, the reactions that take place on the aromatic ring are electrophilic substitution reactions. The OH group attached to the benzene ring activates it towards electrophilic substitution. Also, it directs the incoming group to ortho and para positions in the ring as these positions become electron rich due to the resonance effect caused by -OH group. The resonance structures are shown under acidity of phenols. @ Nitration: 4) With dilute nitric acid at low temperature: -O/P product . The ortho and para isomers can be separated by steam distillation. o-Nitrophenol is steam volatile due to intramolecular hydrogen bonding while p-nitrophenol is less volatile duéto intermolecular hydrogen bonding which causes the association of molecules. b) With concentrated nitric acid: -2,4,6 product . oH on With concentrated nitric acid, phenol is converted to 2,4,6- cone Ho, NOs trinitrophenol ( pierie acid). The yield of the reaction product is poor.Now a days picric acid is prepared by Kos treating phenol first with concentrated sulphuric acid 2eermntmorlenel which converts it to phenol-2,4-disulphonic acid, and then with concentrated nitric acid to get 2,4,6-trinitrophenol. 2, 4, 6 — Trinitrophenol is a strong acid due to the presence of three electron withdrawing -NO> groups which facilitate the release of hydrogen ion. (ii) Halogenation: a) bromine in solvents of low polarity(CHCI; or CS;) and at low temperature: O/P_ product. on ou OH The usual halogenation of benzene takes place in the Br presence of a Lewis acid (FeBr:) which polarises the halogen molecule. fh, In case of phenol, the polarisation of bromine molecule takes ee Maier place even in the absence of Lewis acid. It is due to the highly activating effect of OH group attached to the benzene ring. 266Enrichment Xil CBSE CHEMISTRY b) bromine water: -2,4,6 product . 2,4,6-Tribromophenol is formed as white precipitate. oH 1H Bi Br + 3By—> 2,4,6-Tribromophenol Kolbe’s reaction OH ONa on co, COOH C0 % 2-Hydroxybenzoie acid (alleylic acid) Phenoxide ion generated by treating phenol with sodium hydroxide is even more reactive than phenol towards electrophilic aromatic substitution, Hence, it undergoes electrophilic substitution with carbon dioxide, a weak electrophile. Ortho hydroxybenzoic acid is formed as the main reaction product. 3. Reimer-Tiemann reaction on Ba O Not SHCL, Cito a CHO NaOH, Salicylaldenyde Intermediate On treating phenol with chloroform in the presence of sodium hydroxide, a—CHO group is introduced at ortho position of benzene ring. This reaction is known as Reimer - Tiemann reaction. The intermediate substituted benzal chloride is hydrolysed in the presence of alkali to produce salicylaldehyde. 4.Reaction of phenol with zinc dust: OH O +m =O) + 20 5. Oxidation: Oxidation of phenol with chromic acid produces a ee R conjugated diketone known as benzoquinone. In the aceo, presence of air, phenols are slowly oxidised to dark coloured mixtures containing quinones. Acidity of alcohols and phenols 1. Alcohols and phenols react with active metals such as sodium, potassium and aluminium to yield corresponding alkoxides/phenoxides and hydrogen, 2. phenols react with aqueous sodium hydroxide to form sodium phenoxides. 3.The reactions show that alcohols and phenols are acidic in nature. 4.Alcohols and phenols are Bronsted acids i.e., they can donate a proton to a stronger base (B:). 267Enrichment XIl CBSE CHEMISTRY yy O-R—>B-H + G-R Base Acid Conjugate Conjugate acid base Acidity of alcohols: 1 The acidic character of alcohols is due to the polar nature of O-H bond. 2.An clectron-releasing group (-CHs, ~C:H) inereases electron density on oxygen tending to decrease the polarity of O-H bond. This decteases the acidstrength R R —CH,OH > _ SCHOH> R>c- OH R R° Primary ‘Secondary = Tertiary 3.Aleohols are weaker acids than water because alkoxide ion is a accept proton from water k + HO-H—>R-O-H + :OH Base Ack! Conjugate Conjugate acid base 4.This reaction shows that water is a better proton donor (i.e., stronger acid) than alcohol, and an alkoxide ion is a better proton acceptor than hydroxide ion stronger bases (sodiumethoxide is a stronger base than sodium hydroxide). 5.Alcohols act as Bronsted bases as well. It is due to the presence of unshared electron pairs on oxygen, which makes them proton acceptors. Acidity of phenols: 1.The hydroxyl group, in phenol is direetly.atta¢hed ltd the Sp2\hybridised carbon of benzene ring which acts as an electron withdrawing group by resonance, Due to this oxygen of -OH group to be positive. ae On ‘On CoH on 2. Hydroxyl group attached to an aromatic ring is more acidic than the one in which hydroxyl group is attached to an alkyl group. The ionisation of an alcohol and a phenol takes place as follows: R-6-1 SS R-UF +H On o Eh Due to the higher electronegativity of sp2 hybridised carbon of phenol to which ~OH is attached, tron density di el sreases on oxygen. This inereases the polarity of O-H bond and results in an increase in ionisation of phenols than that of alcohols. 4. In alkoxide ion, the negative charge is localised on oxygen while in phenoxide ion, the charge is delocalised. 5.The delocalisation of negative charge (structures I-V) makesphenoxide ion more stable and favours the ionisation of phenol. 6.Phenol molecule is less stable than phenoxide ion due to charge separation in resonance structures. 268Enrichment XIl CBSE CHEMISTRY Sop 25S 7. The presence of electron withdrawing groups such as nitro group, enhances the acidic strength ofphenol. 8. This effect is more pronounced when such a group is present at ortho and para positions, It is due to the effective delocalisation of negative charge in phenoxide ion. 9 Electron releasing groups, such as alkyl groups, in general, do not favour the formation of phenoxide ion resulting in decrease in acid strength. Cresols are less acidic than phenol. 10. phenol is million times more acidic than ethanol. Some Commercially Important Alcohols Methanol: Methanol, CH30H, also known as ‘wood spirit’, was produced by destructive distillation of wood. CO+ Hy —aasitmdaa> R-CH.OH ‘Methanol is a colourless liquid and boils at 337 K. It is highly poisonous in nature. Ingestion of even small quantities of methanol can cause blindness and large quantities causes even death. Methanol is used as a solvent in paints, varnishes and chiefly for making formaldehyde. Ethanol: Ethanolis obtained commercially by fermentatign, the oldest method is from sugars by yeast. CH22011 + HO" CgHy206 A Coie &/CeH20¢ "> CHS0H + 20, Fermentation takes place in anaerobic conditions i.e. in absence of air, Carbon dioxide is released during fermentation. The action of zymase is inhibited once the percentage of alcohol formed exceeds 14 percent. If air gets into fermentation mixture, the oxygen of air oxidises ethanol to ethanoic acid which in turn destroys the taste of alcoholic drinks. Ethanol is a colourless liquid with boiling point 351 K The commercial alcohol is made unfit for drinking by mixing in it some copper sulphate (to give it a colour) and pyridine (a foul smelling liquid). It is known as denaturation of alcohol.Nowadays, large quantities of ethanol are obtained by hydration of ethene. Ingestion of ethanol acts on the central nervous system, In moderate amount it affects judgment and lowers inhibitions. Higher concentrations cause nausea and loss of consciousness. Structures of Functional Groups Bond angle: tis less than tetrahedral It is smaller because of It is greater than tetrahedral angle (109°-28"), due to. resonance and sp” angle due to bulky group. Ip-Ip repulsion. hybridised carbon. Ethers: The alkyl or aryl groups attached to the oxygen atom are The two groups attached to the oxygen atom are the the same - simple or symmetr. CH O- CoHs different- mixed or unsymmetrical. CH O- CH; 269Enrichment XIl CBSE CHEMISTRY Nomenclature: ‘common names: Alkylaikyl ethers- by alphabetical order for different alkyl or aryl groups. Dialky! ethers - for same alkyl or aryl groups. TUPAC names ~Alkoxyalkane -the larger (R) group is chosen as the parent hydrocarbon. Preparation of Ethers: 1. Dehydration of alcohols -Mechanism- Sy2: Inter dehydration (between the molecule) 2. Williamson synthesis Mechanism- Sy2 I. Dehydration of alcohols: When excess of alcohol is heated with con, H>SO, two molecules condense losing a molecule of water forming ether. The formation of ether is a nucleophilic bimolecular reaction (Sy2) involving the attack of alcohol molecule on a protonated alcohol. CHCH-OH S282. 4 CH3CHo-O -CH:CHy ‘The method is suitable for the preparation of ethers having primary alkyl groups only. The alkyl group should be unhindered and the temperature be kept low. Otherwise the reaction favours the formation of alkene. Limitation: This method is only suitable for preparation of Symmetric ether and temperature should be maintained properly, otherwise forms alkene. 1° alcohols only give ether; if it is long chain 1° alcohols give better yields. 2. Williamson synthesis: i. An alkyl halide is allowed to react with sodium alkoxide give ether (CHsCHy-Br + CHsCHz-ONa — CH;CHp-O -CH2CHs ~NaBr The reaction involves Sy2 attack of an alkoxide ion on primary alkyl halide. Better results are obtained if the alkyl halide is primary. In case of secondary and tertiary alkyl halides, elimination competes over substitution. GHy— Hy cu, 0 ONE + 8, Be sont ben, + Nebr én, én, ii, If tertiary alkyl halide is used, an alkene is the only reaction product and no ether is formed. =CH,+NaBr + CH,OH oH It is because alkoxide are not only nucleophiles but strong bases as well. They react with tertiary alkyl halides leading to elimination reactions. Phenols are also converted to ethers by this method. Eun ghey Limitation: Primary alkyl halide only gives ethers. Phenyl halides do not undergo this reaction hecause of partial double bond character. Application: It is for the preparation of symmetrical and unsymmetrical ethers. Ethers containing substituted alkyl groups (secondary or tertiary) may also be prepared by this method. 270Enrichment XIl CBSE CHEMISTRY Physical Properties: 1. The C-O bonds in ethers are polar, and thus, ethers have a net dipole moment. 2. The weak polarity of ethers does not appreciably affect their boiling points. 3. The large difference in boiling points of alcohols and ethers is due to the presence of hydrogen bonding in alcohols. 4, The miscibility of ethers with water resembles those of alcohols of the same ‘molecular mass. 5. This is due to the oxygen of ether can also form hydrogen bonds with water Eg Se ON Chemical Reactions: I Cleavage of CO bond in ethers with HI II, Electrophilic substitution (@ Halogenation (ji) Friedel-Crafts reaction (iii) Nitration I. Cleavage of C-O bond in ethers -with HI The cleavage of ethers takes place with concentrated HI or HBr at high temperature, Order of reactivity: HI > HBr > HCl. The cleavage of C-O bond in ethers takes place with hydrogen halides gives alkyl halide and alcohol. In excess of hydrogen halides gives two alkyl halide molecules. R-O-R+HX—> RX+ ROH R-OH +HX —>R-X+H,0 1, Primary ethers: Mechanism - Sx2 Step 1: The reaction takes place with HBr or HI because these reagents are sufficiently acidic. u HCH, +H Z cH,-O-CHLCH, +1 cH,-O- Step 2: Iodide attacks the least substituted carbon of the oxonium ion and displaces an alcohol molecule by Sy2 mechanism. Formation alkyl iodide depends on the nature of alkyl groups. When primary or secondary alkyl groups are present, itis the lower alkyl group that forms alkyl iodide (Sy2 reaction). H. H. Fr ’ : When HI is in excess and the reaction is carried out at high temperature, ethanol reacts with another molecule of HI and is converted to ethyl iodide Step 3: Lo 4 cucu, 9-1 + WY = cHcH—on + on, Xu, Cs — CHCHI + 1.0 2Enrichment XII CBSE CHEMISTRY 2. Tertiary ethers: Mechanism —Sy1 cH, cH. When one of the alkyl groups is a tertiary group, cy -¢ 3 —crr, > cu,—d* = cron the halide formed is a tertiary halide. It is because | oH 1 the departure of leaving group creates a more i. cH, stable carbocation cH, CH, 1 fast 1 cH-ct + 5 — + cH,-c-1 bh, oy, 3. Alkyl aryl ethers The reaction yields phenol and alkyl halide. O-R on The bond between O-CHs is weaker than the bond between O-CsHs because the carbon of phenyl group is +H-X——_> +R-X_— sp" hybridised and there is a partial double bond character. Therefore the attack by I- ion breaks O-CHs bond to form CHI. Phenols do not react further to give halides because the sp” hybridised carbon of phenol cannot undergo nucleophilic substitution reaction needed for conversion to the halide. 2. Electrophilic substitution: The alkoxy group (-OR) is ortho, para directing and activates the aromatic ring towards electrophilic substitution. G5 -—5-6-S (@ Halogenation: ocn, oon, ects ein Br Anisole i pBromoantsole o-Bromoantzole (ii) Friedel-Crafts reaction: sony ocr pen pen. Ethanevi 2-methoxy- 4-methoxy- chloride acetophenone acetophenone (iii) Nitration: OCH; OCH, OCH 1.80, Nos TINO, NO, 2WNitroanisole —4-Nitroanisele 272Enrichment XIl CBSE CHEMISTRY Wt Ans. 112 Ans. 113 Ans. 114 Ans. 115 Ans. NCERT EXAMPLES Give TUPAC names of the following compounds: @ chen en-ex-cu.on Co) CH, ~CH-O-CH,CH, & dd, | CF OH Ni H.C . I JH _/ 0G,H, (it) ‘) tiv) i () 4-chloro-2, 3-dimethylpentan-1-ol (i) 2-Ethoxypropane (ii) 2, 6-Dimethylphenol (iv) 1-Ethoxy-2-nitroclohexane Give the structures and TUPAC names of the products expected from the following reactions: a) Catalytic reduction of butanal. b) Hydration of propene in the presence of dilute sulphuric acid. ¢) Reaction of propanone with methylmagnesium bromide followed by hydrolysis. (a) CH,-CH, -CH,-CHO +H, —““*™ CH, —CH, -CH, -CH, -OH ©) cH, -CH-CH,+H,0 4% cH,-CH-cH, Propane - | OH Y CH, © é Y HH 0 + CHMgBr CH, —c —o|MgBr / | Propanone Motiyal magaesiam cH, cH, Br HO (hydrolysis) cy, Gon + Mg—oH cH, Arrange the following sets of compounds in order of their increasing boiling points, a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol, methanol b) Pentan-1-ol, n-butane, pentanal, ethozyethane. (a) Methanol < ethanol < propan-1-ol < butan-2-ol -CH— CH,O MgCl | t CH, CH ‘ (9 HCHO + CH-cH—Mgc! q CH, -CH-CH,OH + Mg-OH CH 2amethyipopanal HOH MgCl CH,O/MgCl CH,OH Ce 10 HCHO + —_— a +Mg-OH Write structures of the products of the following reactions: Hom t CH.-¢—ocH © CH-CH = \ @ —G—OCH, _NaBH CH;-CH =CH, EG GO ° NaBi CH= CH CH—CHO CH, © CH= CH—CcH, -224".cH,—CH—CH, 0 OH CH-C—OCcH, N88 | CH-C—OCH, Vs ° U fe} CH> CH;-CH—CHO _N@BH. | CH.— CH CH —CHOH CH, CH, Give structures of the products you would expect when each of the following alcohol reacts with (a) HCI+ZnCh, (b) HBrand (©) SOCh. @ Butan-1-o1 (i) 2-methylbutan-2-01 (a) With HCI + ZnCh, (Lucas reagent) 276Enrichment XIl CBSE CHEMISTRY () CH,CH,CH,CH,OH + HCl "5 CH,CH,CH,CH,Cl+H,0 att (ons) ett cH, CH, (i) CH, 5 CH,CH, + HCL ee CH,- C-CH,CH, oH cl 2 ety 2h stiyatase (b) With HBr (i) CH,CH,CH,CH,OH + HBr —“"> CH,CH,CH,CH,Br +H,0 om CH, zal (i CH, -¢-CH.CH, + HBr #5 CH,-C-CH, CH, +H,0 OH Br Metal 2202s (©) With Soc, 0} CH,CH,CH,CH,OH + SOCI, —“4 CH,CH,CH,CH,CI + SO, 7 + HCI t CH, cH, (ii) oH -¢ cH,CH, +SOCI, “+ CH, - C-CH,CH, +80, 7 +HCIt OH cl 11.7 Predict the major product of acid catalysed on dehydration of (i) 1-methyl cyclohexanol, and (if) buta Ans. , CH, CH, CH, @ ¥ OH To? + |-mshylefohessnol antl eeloexene |-methylneeyetohorane Mon) (Min) (i) CH,CH,CH,CH,OH —j!2> CH,CH=CHCH, + CH,CH,CH=CH, 27Enrichment XIl CBSE CHEMISTRY 11.8 Ortho and para nitrophenols are more acidic than phenol. Draw the resonance structures of the corresponding phenoxide ions. Ans. The nitrophenols are more acidic than phenol, because of the effective delocalization of negative charge in the phenoxide ions of nitrophenols. Their acidic strength due to— Resonance effect of NO2 group o- and p- nitrophenoxide ions more stable because of additional resonance structures. Phenoxide ion have negative charge on the carbon atom is which the electron withdrawing nitrogroup is attached, As a result, o-and p-nitrophenols are more acidic than phenol, Resonance structures see notes. 11.9 Write the equations involved in the following reactions: (i) Reimer Tiemann reaction (ii) Kolbe’s reaction. Ans. See notes 11.10 Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane starting from ethanol and 3-methylpentan-2-ol. Ans. H,OH + HBr —> C,H,Br + H,0. CH, CH, CH-CHOH —*+ CH,CH,CH-CHONa ch, cH CH, CH, CH,CH,CH —CHONa + C,H,Br —.,->CH, CH, CH-CHOC,H, Io CH, CH, CH, CH 1 decoy pee 11.11 Which of the following is an appropriate set of reactants for the preparation of 1. methoxy-4-nitrobenzene and why ? Br ONa @ (i) + CH,ONa + CH,Br NO, NO, Ans. Both sets are equally probable: In set (9: Nitro group is highly deactivating in nature, it will make the cleave of C—Br bond very easy. Since the electron density on the earbon atom has been considerably decreased, so the nucleophilic attack by CHsONa followed by elimination of NaBr gives the desired ether. Br OcH, (CH,O-Na* ss + NaBr No, No, “Niteobromobenzene 4:Nitwomisole 278