Second Edition

OR~INIC

~~~l{?~~

CHEr,iISTRY

PROBlEMS AND SOlUTIONS (FOR 1.1.1. AIEEE. ENGINEERING

& MEDICAL ENTRANCE EXAMINATIONS)

RAJ K. BANSAL RAJIV V. BANSAL

!f.tl NEW AGE INTERNATIONAL rUALISHERS

1 1

Cop)'richt C 2006, 1999 .• New Age International (P)Ltd., Puhliahen Publlahed by New Ap International (I') Ltd., Publishers

Firat EdItiOD. : 1999

Seaond Edition : 2000

All rilhlll.--i

No part of tIWo book mar b;o reproduald In "OJ' &>nn. by phoIoRat, mierolilm, ~,<6 my..u- ......... orinoorporatediDl:o azJ3infi>noat1ooretrieY&l .,._, eIeetn>nic or.......tlaDiad. without tile wriltel! permiMion altlle <OPJriIht _.

ISBN ,81-2S4--17117-3 Ba.22IUIO C-05-10-.30

Printed in HlndUItaD 0I&et, Delhi. ~.Goowaml.Printer, Delhi .

........... OO! OI.-.WQRLD

NEW AGE INTI:RNA1l0NAL{p) LlMlTED,PI.lBLISItE.RS fw-ft 1r.V&atnu../J

'13'124, II....., Rood, Doryapnj, New Oc!hi • II 000l Vi';I"II __ ,,~

U rhcberrec htl lch gesc h utztes M ateri a

CONTENTS

Preface ; (I')

1. Electron and. the Chemical Bonding , 1

2. Nomenclature of Organic Compounds , 13

3. Factors AlfecUng Acid Base Slrengths 21

4. Stereochemistry '" 33

5

8eactJon Intermediates and Mechanisms

55

6. Purification and Structure Determination of Organic Compollnds 63

7 Alkanes as

8 Alk,enes 102

9. Allcynes 129

10. Polymers 154

11. Cycloalkanes 154

12. Aromatic Hydrocarbons ,_ , " __ 168

13. Organic Halogen Compounds , 189

14 Alcohols and Phenols 217

15.. Ethe rs and Epoxldes 242

16

Thjnls and Tbjoelhers

254

17. Aldebydes and Ketone.a _ _ 259

18. Carbo_ylle AcidS 289

19, Functional Derivatives of Carboxylic Acids , " , " , _ 310

20, Sulfonic Acids. Their Derivallves and Drugs 346

21. Amlnes and. Nitro Compounds _ 354

22.

Organometallic Compounds " , _ _, " " "' "' 387

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23. Heterocyclic Compounds ' , 399

24. CaJbohydrates 412

25. Amino Acids. Peptldes and ProteIns 432

26. Terpenes, 449

2,7 . Pericyclic Reaction s , , 45 6

Inder

464

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I CHAPTER I

1

Electron and the Chemical Bonding

Problem 1.1:

Describe the following terms:

Polar bond, bond angle, IIMOciation, eiociropollitive elements. formal charge, bond length, bond dissociation energy, molecular dipole moment, atomic orbital, molecular orbital, bonding and anti-bondlng orbitals.

Solution: Polar bond: A covalent bond in which there is an unequal sharing of electrens between tbe two bonded atoms is called apolar bOlld. A bond with equal sharing of electrons is called a nonpolar bond.

Bond anale: The angle subtended by two bonds joined to an atom is called bond angle.

The bond angJedetermin""the shape ofa molecule whether it is beat or linear .. A bond eihibiting different type!! of hybridization also forma different bond angles. Bond angle is II property of a bond similar to bond energy and bond length. A bond angle cannot bo predicted by uBing the simple B and p orbitals alone.

AoosociaUon: The intermolecular hydrogen bonding in e liquid results 'in its huge molecular aggregate,. This iB ref ...... ed to n. assoeiation. . The ...... o.istion of liquid molecules causes an increase in its boiling points.

Eleatropositive elements: Those elements which have low eleotronegativity (or have a tendency to lose an electron) IU'e eleetroposittie.

Formal chllrfe: A mothod for keeping track Olf charges,.howing what. charge would be on an atom In B particularLewis strueture is caned a (ormtl/ charge.

Bond len¥lh: BOlld kngth is the internuclear dlstanee between the two bonded atoms.

It is expreaaed in angBtrom. units rJJ. Tho bond length is obtained by electron diffi'aotion and X-ray diffrnction techniques. The magnitude ofbond length depends on several faetora such BlI hybridization and resonance effects.

Bond dluocia tion anergy: It is the energy required to break a bond to produce two

. fi'ce radicals. .

Molecular dipole moment: The vector sum of the individual bond dipole moments and any non bonding pairs of electrons in a molecule is called molecular dipo"" mo""mt. It is a. measure of the, polarity of a molecule.

Atomic Orbital: It is a region in space wbere an electron ia likely to be found.

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2

Organic ClY&mislty-P ,~em. and Solutio,,"

. Mole<lular orbital: An orbital formed by overlap of atomic orbitals on different atoms is called a molecular orbital.

Bonding orbital: A molecular orbital which has lower energy and greater stability than the atomic orbitals from which it Is formed jJj known as bonding molecular orbital. A bonding orbital forms a a-bond.

Anti·boudinr orbital: A molecular orbital which hIlS higher energy and lower stability than tho atomic orbitals from which it i. formed is known liS antt-bondlng orbital. Such an orbita! forms II aO-bond.

Problem 1.2:

Write 8 Lewis structure for each of the fullowing:

(a) Methylamine (b) Ethyl anion (e) Propanol (d) Acetylene (e) Acetic acid (fJ Ethyl. magnesium chloride.

i;I

H H

Solution: (a) H"9"~"H (b) 0"9"9:' (c)H"9"9"¢"Q"H (d)H"C::C"H

HH flU HHH

H :0: (e)H··9··g··R"H Ii

Ij fj

(fJ H·· 9"9 "Mg" ~!:

H H

Problem 1.3:

Indicate the polarity of the bonds between the atoms within the bo" of the following compounds,

r---'----.

(a) CH.t:'~~.!

Cl

·t····,

(b) CJ-l-C-Cl: :-t- ----:

Cl

(dJ:Ci-I: ~-----.!

"'-~-------I

(e) CH3CH2CH,+CH.-Li:

1 ----,

....... -"' .... --

CIl H3c+c-e-.!-cHa

... _----_!

Solution: In 8 polar bond, a pair or electrons is shared between two atoms with unequal attraction.

(a) Polar (b) Polar (d Polar (d) Polar (e) Polar (f) Non-polar.

Problem 1.4:

Predict the hybridization and geometry of the following molecules;

(a) NF3 (b) CaH6C-CR (c) ~O (d) CHaCHO.

Solut.ion, (a) sp3, tetrahedral (b) .p, linear (c) .p3, tetrahedral (d) .p~, pyramidal. Problem 1.S,

Show by B crossed arrow the direction of dipole moment of the following molecules: o

II

(a) CHsCCHs (b) CHaBr (e) C2HsN~ (dl S02 (el CHaN02'

Urheberrechtlich geschutztes Material

EIect,on and the C hemlCal Bonding

3

n __ -+-+; 4S~ __

Solution, (a) CHs-C-CH, (b) CHr-Be (e) C2H,-NH2 (dl ° 0 (el CH,~NO.

Problem 1.6,

lndieate which of the following pairs of ccmpounda is higher boiling;

(a)CHaCa_CHNH2 or CH3C~NCH3 (&)\.I'\/'\/0H or

I I

CH3 CHa

(e) CN_:H or ONH.

VXOH

Solution: (Il) These are isomeric amines but CHaCH.CHNH. being a primary amine can

I

CH.

form Il-bond, It is thus high boiling. The 3' amine lacks a H-atom on N.

(&) These ore isomers but the primary alechol can form better H-bond and thus the, former alcohol is hlghboiling.

(e) Cyclohexylamine (i) for the same reason as above ean form better H.bond and is high boiling.

Problem 1.7,

Which of the fellowing compounda can from hydrogen bonda with water? o

II

(&) CHaCNH.

°

(0)(1

([laOH

Solution: (Il), (b). (e) and ([l can form H-bondwith water, but (d) and (e) cannot, In tho latter two campounils one is 3· amine and the other ia a hydrocarbon.

Problem 1.8,

Distinguish between a-orbital, p-o.rbitai. 'P. sp' D.Ild spa hybridized orbitals. Give enmplee.

Solution, • .orbital, An s-orbital is syrn metrical abo utthe nucleus and has a quantum n urn ber 1= O. The sign of 10 wave function is everywhere positive. For hydrogen the Ls atomic orbital is involved in bonding. For other elements such lIS sodium. lithium. carbon. oxygen. chlorine.s is always filled and ill not involved in bonding.

p-Orbital: Ap..,rbito1 is not symmetrical as thas-erbital. It rather eonaists of two lobes with II nodal plane at tho center. For eachp-orbital the quantum nmnberl equels I. These arc three in number i .e., P.,P~ and p •. Examples of hybridized orbitals are given in the table.

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4

Organic Chemistry---f'robIema and Sotutlon&

s+p • +2p

Lin.e_r

TriiOnol planar Tetrahedral

180' 120'

BeCl" Calil ' lIgClz SF., NOi ' C,lI •

CR., N~ ,BH" SaC),

Atomic oroitolr

BOlld ""8"

bmpl.

• + 3p

109.5'

Problem 1.!I,

Intramolecular hydrogen· bonding o.:cUI'S incis·l, 2·cyclopent.n.ne<!io] but not in thetrans· isomer. Why?

~

H H

~

H OH

cis trans

SolutioPJ In ci8-diol, the hydroxy groups are close together while in thetrans.isomerthey are too far apart. The hydroxy group.i! in the fonner structure thug call fClml hydrogen·bond easily.

Problem 1,10,

c-Nitrephenol i. steam volatile and lesasoluble than its other isomers. Why?

Solution, Duo to intramolecular hydrogen·bond formation mo·nitrophonol, tho intermolecular association is reduced, this make. it more volatile. Conversely because of int ra molecular hydrogen-bend, e-nitrophenol is incapable of forming hydrogen·bond with water and is thus leas soluble in, water compared to the other isomers which can Hsbond with water.

Problem 1.11,

(0) p.Nitronniline has II. dipole moment (6.10 0) greater than the sum of the dipole momenls of nitrobenzene (3.95 D) and aniline (1.53 D). Explnin.

(6) Explain the differente in the dipole moment of the following compounds,

C~CHO WId CH~CH=C~

II'" 2.66D

II"O.3ftD

(c) Which of the fOllowing two compounds will have a larger dipole moment and why?

CHaN 02 Or C&HsN02

Solution, (0) The direction of dipole moments in these compounds is as follows;

~NH.

9

~NO.

~NH. tND,
~ (6
1,=1.53 D ~=S.95 D ~=6.H'D

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Electron and Ihe Cl\emlcal Bonding

5

The dipole moment values for nitrobenzene and aniline show that NH2 and N02 groups induce dipole .moments in opposite directions with respect to the benzene ring. In p-nitrcaniline the dipole moments of these group .• reinforce each other to lnerease the net value.

H I

(/:I) There is more charge eeparationin acetaldehyde (Cl'a- C· ......0-) than it is in pro-

pene (CHs-eH-CHj;). The larger e value th1l8 iuc:reaoe. dipole memant.

(c) Nitrobenzene would have a larger value of dipole moment than .nitromethano because of a greater distance (d) of charge (e) ~epara.tion, the dipole moment = d M: e.

Problem 1.12:

Describe formal charge and calculate the formal charges on the atoms indicated in

parentheses.

H~O.(S and 0), calc and 0),. HCOii(C and 0), CHi(C and H), Cf'aO-(C, H and a), Cf'aOH(C. H and 0), : CF~(C and F).

HCOi(C, Hand 0), C~N~(C and N), NH~(N). HsO·(O). BF4"(B) SolutioD: Formal charre: The Lewis structures described earlier are tbose of neutral moleeulea. But many ionic "peciee such aa BF7 ' H30· also contain covalent bon de:

:P:

[.. I .. ]-

:F-B-F:

.. I ..

:F:

Telnol'luoroborateloo

Since the ion hili! a negative ch"l'ie. one Or more atoms within the ion must be chargedbut which on.01 The charge is nonnally sbared by all the atoms. A useful procedure has been adopted for electronic book-keeping that asstgns a charge to apeeifle atnme. The charge on each atom thll8 lIS,igned is called its formal charge.

Note that th.e sum of the·formal chargee OR the individual atoms must equal the total charge on the ion.

The formal charge on en atom can be calculated by the following equation:

Fonnal charge = Valence electron. of the isolated atom

- [ unshared electrons + ~ (shared electrons)]

S=6 - [0+ ~(12)]=O 0=6 - [4 + i(4)]=O

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6

Organic Chemlslry-Problema end SoIullon$

CH3 C=4-[1+~(6)]~O

H=1-[o+i(2)]=O

CHaOH G=4-[O+~(S)]=O

H=1-[O+~(2)]=O O=6-[4+i(4)}-0

HCO; C=4-[0+~(8)]=O

H=l-[O+~(2)]=o 0=6 - [6+% (2)]=-1

CHa0- C=4 - [0 + ~ (8)]=0 H=1-[0+~(2)]=0 0=6 - [6.+%(2)]=-1

,CF1 C=4-[2+i(4)]=0

.F=7 - [6 + % (2)J=0

CHaNlf:l C=4-[0+%(S)]=0 N=5-[2+%(S)]=0

H

I

H-r-H N=5-[O+~(8)]= + 1

H

H H

I I

H-r-r-'-H N=5-[0+~(S)l- + 1, B';_'S + [0+%(8)]--1

H H

(a neutral moleeulel

H_Ff

H-T-H O=6-[2+i(s)]= + 1 H

Neutral moleculeto han ....... formal chaqe. problem 1.1S:

The central bond ofbiacetyiene is 1.37 A. wbe reas a normal C-C bond distaDce is l.54 A.

Hew do you acceun t for this dillerenee?

Soluticm: Because the following type of orbital overlap eausea the CaD.tral C---C bend to be shortened.

Urheberrcchtllch qeschutzzcs Materi"

7

1 2 3 (

H-C-C--O-C---H

Problem 1.14:

How do the bond lengths and bond angles vary in the following eases?

I -rHo

I I -C-O-.

I I

I -O-CI I

Solution.: C--H, O-C and C--Cl bonds are sp3 byhrid.ized., therefore, they would be longer than. C=C and. C"'C bonds. The former set of compounds will have an angle ofl09.S· whereas the last two nn angle of 120·.

Problem l.lli:

Ex-plain what is meant by dipole moment? Name two compounds which show dipole moment and two which do not.

Soll.tion: Dipole Moment: Certain covalent bonds are polar. A bond which. has any degroo of polarity will have a corresponding dipole moment, The dipole moment abbreviated. by the letter II of a dipolar molecule (a molecule in which-the eenters of positive and negat.ive charges an! separated) is defmed as the product of the charge (e) at one center and the distance (d) between the negative and the positive centers. Dipole moment Ism<pre!!llcd in terms ofe.s.u. Ol' the Debye unit abbreviated. D. Debye being equal to dipole moment of 1 >< 10-18 e .s, II .• cm/ molecule. All dipole, moments are of the order of 100IS e .s, u.

lI=e><d

CH:,NH2 and CHaOH possess dipole moment while CCI. and troJiS-2-butone do not.

Problem 1.16:

Why is it necessary to invoke 8p2 byhridizatioll to explain bonding in C2H.?

Solution: C2H. contain.s a carbon-earbcn double bond in which' a carbon atom is bonded to only three other atoms and hence ~p2 hybridi.zation takes place.

Problem U7:

Predict the direction of the dipole moment, if any, in the following molecules: tel, Br2, HCI. a.z

Solution: Br2 and ~ bnva no dipole momcnt whereas ICland HCl do. The dipole moment vector points towards CI both. in ICI and HCI.

-

I-Cl

...._

H-Cl

Problem 1.18:

Which C-C slngic bond .;6 shortest in length among the following?

CH3-CH2-CH~, CH3-CH=CHl, C~C-C-C""'CH, CH3-C.:.GH

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8

Organic ChemiSlry---f'robIems and Sol\JtiOns

Solution: The C-C band is shortest in CHsC-C-C-CCHa because, the C-C bond earoons are 8p hybridiud.

Problem 1.19:

Predict the Shape of the following molecules:

BeCl2 • NH: • ":a0. BCl,. SiFt ' PHs

Solution: Linear, tetrahedral, tetrahedral,trigonal planar, tetrahedral, trigonal planar. Problem 1.20:

Warer has a dipole moment but carbon diozide has not. E,.plain.

Solution:

~

H 11l<1.S' H

...... _ O=C=O

In water there are two O-R bonds which are polar and inclined at an angle of 104.5'.

The two bond dipoles do n,ot cancel and the vector sum of bond dipoles give a resultant dipole moment.

The CO2 molecule, on the other hand, is linear. The C-O bond dipeles are oriented in opposite directions. Since they also have equal magnitude, they eaneel. Therefore CO2 hili! no dipole moment and is also non-pillar.

Problem 1.21:

Give an example of an element that undergoes sp hybridization in forming covalent bonds with other elements. What is the value oftha angle between, the bonde that result from 8 - sp overlap of atomic orbitals.

SoluUon: Th,e element is carbon. Th,e angle is 180'_ Problem 1.2Z:

Why doe. ice contract, when it melts?

Solution' The hydrogen bonds formed between water moleeules hold them in an "'open n.tworkstructure in the ice crystal. As the ice malts, hydrogen bonds are broken and the resulting liquid occupies Jess space than the original solid ice, leading to ita contraction.

Problem 1.23: What shape would you e.xpect, the following to have?

(0) CR; (b) CHaNli.i (el CRi {d} (CHa)s B (el BF;j" if) lI:!S (8) CHsOR (h) NHi Solution: To arrive at the shape of a molecule, We need to know how many orbitals the central atom can hold (not "nly the atoms alone attached to i~ but alsounshared pair of electrons.) If it ho.lds four orbitals then it is Sp3, if three than 6p2 and irtwo tbensp. The shape given below in each case refere to if unshllTCd pair of electrons oro included and then if only atoma are included (thia ill given in parentheses],

(0) TrigonRi like BFa

(trigonal because three are three hydrogens).

""~C......_

',./ <,

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Electron and the Chemical Bonding

9

(b) Tetrahedral like NH3

(pyramidal with tetrahedral angles)

(e) Trigonal pyramidal like NRa (tetrahedral with tetrahedral angles)

CH"..,...../···:s~

S CRa

CHs

v

C

'1"

(e) Tetrahedral like CH. (tetrahedral)

F

I

B

/,,""F

F F

(g)"Tetrahedrallike H:!O

(nat with a tetrahedral angle)

R

H \ »:

/C-O~

H

~ .. »: /'b-N~

(d) Trigonal like BF 3 (trigonal)

if) Tetrahedrnllike ~O

(flat with a tetrahedral angle)

I

;

s

/'t":

H H

(h.) Tetrahedral like ~O

(flat with a tetrahedrol angle).

t H''1~:

H

Problem 1.24:

Explain why CHaCI (1= 1.90 D) and CH~ (1= 18.6 D) have id.entical dipole moments at though fluorine is more electronegative than chlorine.

Solution: The magnitude of dipole moment depends not only on the amount of charge (e) that is separated but also the lfurtance between the charges. The C-CI bond in CHgCJ and the CF bond in CHaF havo the same dipole moment because the large bond distance of C-CI bond and the higbeJectronegativity of F atom compensate each other. This results in both the molecules to p<>I!l!el!8 the same dlpelamoment,

Problem 1.25,

Arrange the following in the order of decreasing bOnd energy:

H-F. H--(:I. H-Br, H-I

Solution: H-l < H-CI < H-Br < H - F

Large size and lower electrenegativity of balogen makes H-I bond longer and weaker.

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10

Problem 1.26,

What are hybridized orbitals? Justjzy the intrcductien of the concept of hybridization in "orne cases. and give an example of each type.

Solu tlom Hybrid orbital. are degenerate orbitals formed by mixing of orbitals differing in small amounta with each other, in energy. 'The concept of hybridization allows the "eonstructien" of new orbttala on atom", so that the bOnding in a molecule is made conslsteut with ita known goom.ctl'y. For example, in BeHv the geomatry is linear having bond angles of ISO". The two B.,.._.H bonds also have same bond lengths. Now, the electron co.nfiguration of Be atom is 182 ~.lfit is to form two bonds by sharing one electron with each of two other atoms then it must first be put into a state where eaeh electron is in a different orbital, and each spin is uncoupled from the other and thus is ready to be paired with the spin of an eleetrnn on the atom to which bond is to be formed. Although t,he promotion of the Be atom to the valence state (unpaired spin state) prepares it to form two lxlnds to the H a toms it does not provide an, explanation or a reason why molecule should be linear rather than bent. The 2s orbitals of Be he ve the same amplitude in all directions. Therefore, whichever of the 2p orbital" is used to form one S.,.._.H bond, the other bond in w hieh 28 orbitals is used could make, any angle with it, in BO far as overl ap of H and Be 211 orbital is ceneerned, However, the preference for a linear structure can 00 attributed to the faot that if 2s and 2p orbitals Are mixed so as to form two bybrid (i.e., milld) orbitals, better total overlap with H 18 orbitala can be obtained, Similarly planar character of BeCIs molecule with bond angle of 120' can be explained by in trod uetion of 8p' hybridi .... tion, The boron atom (electroni c configuration 182 2112 2p, !) in the groundstate can be promoted to boron a tom in exei tedsta te (electronio configuration ts2 2s 1 2p, ! 2p y !). Orbi tale in the excited state are mixed to form 3sp i orbitals of equal energymRking an anglo of 120' with each other, Hybridiz.a tion also controls molecular shape, The tetrahedral nature of methane is explained by evolving .p3 hybridization at carbon.

Problem 1.27:

Describe the formation and shape of an spa hybridized. orbital.

Solution, In carbon atom one electron from the 2s orbital ts promoted in the excited state to the vacant P, orbi tal 88 shewn below:

is 211 2p, 2py 2p,

C(excited state) H t + t t

Now, mixing of 2s, 2p" 2py, 2p, orbitals occurs to form four new equivalent orbitals called the hybridized orbitals containing one, electron each, These four hybridized orbitals point towards, the four comers of a tetrahedron. The tetrahedral geom"try ia favorable for methane because the four bydrogen atoms and the fOUT pairs of bonding electrons are as far apart as possible from one another but 'Still close enough to form covalent bond. The shape of an sp' orbital ie shown below and. it consists of two 10 boa, one large and one 8m all. It is only with the large lobe that any appreciable overlap takes place,

z

¥--

Four ~p' h:!brid "rbilal.

~9. Y!fij .. '

2p.

2p,

U rhcbcrrec h II ich ges" h utz tes ~ t ~tcri"

Electron and the Chemical Bondi'lg

11

Problem 1.28:

Why do we not use the, threep-«bitals (2p., 2py' 2p.) alone to fonn the three equivalent hybrid orbital" "d. carbon?

Solution: In general We should construct hybrid orbitals from. the lowest energy atomic orbitals available. 'This involves the bonding electr00.8 to have the lowest pessible energies. The 2s orbitals are, of lower energy than the 2p orbitals.

Problem 1.29:

Define a a bond. HOw is a earben-earbon a bond fonned? ~y is aft bond weaker than a " bond?

Solution: Sigma bonds are the mO!!t common beada in organic compounds. The, type of bond formed when the molecular orbital has its electron de,,"ity eente~ alcng Ilie line coanecting the nuclei is called 11 " bond. A" bond ill formed by the overlap of two hybrid orbitals along the internuclear axLo. For instance. the sp8 hybridized orbitals nt two carbon atoms overlap to form a earbon-earben a bond.

Every double or triple bond ... otains one a bond, A double bond results trom the overlap between the p-orbitals oriented perpendicular to the nuclei connecting them. This lateral overlap is not as effective W! the overlap along the internuclear w •. Therefore. a " bond·iI! weaker than the a bond.

Problem 1.30:

Which of the atoms in each of the following has a complete octet?

NH,. :CHi. CH •• BH3

Solution: Only CH •• because, all the four valeneiea of C are satisfled. Problem 1.31:

Predict the approximate bond angles in each of the following mcleeules,

.. + -=-

CH!. :CCI2• Be14. Q=Q~Q:. CH2=C=CH2

(own,,)

Solution: CH;

8p2 hybridized. 120·

:C/CI "Cl Ozone

BelJ2 sp bybridi~ed. 180'

CH,=C=CH2 Linnar.180·

Probll!ml.32:

Select the eomJd. answer.

(a) The type of hybridization ezhlbited by each carbon atom in

SimilartoH.p.l04·

A.. sp end sp

B. 8P~ only

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Organic Chemi~rtlblem!l IIIld Solutions

(bl In the eompound CH.=CH--CH.-CH2-C-CH, the C2--Ca bond is of the C:ype:

A. $P - Sp2 B. sps _spa C. sp _spa D. ,p2 _spa

(c)' Which of the following hydrocarbons have the lowest dipole moment?

CH., /CH.

A. /O=C, B. CHa -C-C--CHa C. CHs--CHz-C""CH

H· 'H

D. CHI=CH--C"'CH

(d) Which of the following rep", ... nt the given mode ofhybridlution?

Sp2_ ,p2 -sp _ $P

A. CH.=CH-C-N B .. CH1=CH--CH=CIf:, C. HC-C-C-CH

D. CHFC=C=CH

(e) The CI-C-Cl bond angle in 1, 1, 2, 2-tetraohloroothene and tet.r.ichloromethane will be about:

A. 120" and 109.5° B. 90 and 109.5° C. 109.6" and 120" D. 109 .. 5' and 90" if) Pick out the teoeleetrnnle structUre8 from the following;

ca;, CHi, NHa, R:ao+

A. ca; and HaO· .B. NHs and CHi C. CR; and NHs D. Ha0·, NHa and CHi. (g) Select, the COJTe<:t order of decrea"ing energy.

p, sp, sp., sps

A. P > $P > sp' > sp" B. $P > Sp2 > sps > p C. p > Sp3 > ~2 > I1p

D. sp3> IIp. > sp > p

Solution:(a.)C (b)D (clB (d)A (elA (flD (g)C, the more thes-characterin an orbital, the lower is jta energy,

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I CHAPTER I

2

Nomenclature of Organic Compounds

Problem 201:

Describe briefly the rules ofIUP AC sy.stem of nomenclature for saturated hydrocarbona. &lution: The following rules are followed to translate a structure into a name and uice uer8l1.

1. The generic name rOlr parBf'fina or saturated hydroc:arbona is alko,Ms.

2. In 8 compound to be nam.ed, first determine the !ongeststraigbt chain of oontinuous carbon atoms. The name of the hydrocarbon is assigned by counting tho number of carbon atoms in this chain. Th.e selection of the carbon chain does not. depend upon how it is written. Each of the following chains consist of seven carbon atoms and correspond to heptane.

,~ ~1

H 5 7 ~

, 4 5 7

3. To specify the positions of the substitu(l,nta, they are given names and numberaThe name of the alkyl substituent is derived by cbanging tbe paraffin h,ydroearbon ending -one to -yl.

Th.e carbon chain ill numbered eommeneing' at the end nearest the branching if any. Thill is done to 8IIsign the lowest number to the substituent or group attached to the chain.

2-Methylhexane (written as one word)

2,2,4,4,6,8,8-Hepto.methyinonano

13

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14

Organic Chemlstry-Problems and Solutions

4. When the carbon chain bears two similar aubstituent!!, their loearions and numbers are represented by prefixing <1;.(2), Iri~3), telru-{4), etc.

XA/

1 a e

)zA_.J.-..

7/ Y A '1

2,2·Dimethylh~ne

3,3,6- Trimethylheptane

5. When two or more eubstrtuenta are present in equivalent poBitiona in the carbon chain, the lower number is aaeigued to that group which is written fint in the name of the compound in the alphabetical order,

3· Ethy 1·'7 ·methy lnonane

6. While writing the name of the compound, write the substituents in en alphabetical order, i.e. ethyl before methyl.

AAA

1 iI ~7

5·Ethyl·2·Plethylh~tsne

7. A complicated branched chain is named as a derivative of the longest chain (i.~. the base ehainr-in thet compound. Thia chain ill numbered ,.t.artmg from the carbon chain linked ID the base chain. Its name is constructed On the basis of IUPAC rules and is enclO!led within parenthe&is to distingui8h it from the base chain.

a 6 • 2

/~'

2

S Il 4 2

~~1 . '~3

2

3.(I-Methylpropyl) nonane

Problem 2.2:

Suggest IUPAC name for each of the following hydrocarbona :

(l»\.,>{: J..... ) yvy Is

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15

,2 4 S B

1~.79

if) ~

2 4

II

12

10

16

.'

(h)

7yf.231

4

01 6

(i) 12 (Va

l/Y[V

Solution: (a) 2,3-Dimethylh.exane (6) 3,3,6- Trimethylhe.ptane (e) 3-Et.I\yl-5,7-Dimethylnonane (d) 3,4-Diethyl-2,7-dlmcthylocatan,o (c) 5·( l,2.,2-Trimethylpropyl) nenane (f) 3-(1-MetbylbutyJ) nenana VI) 6,6-Diethyl-4-methyldeco.ne (h) 6-Butyl-7-methyldodeco.ne (i) 4-Ethyl-2,1),6,6- tetrametbyloctane \J) 4-bopropyl-3-methylhsptane (k)4-Isopropylheptane.

Problem 2.3:

Write briefly the IUPAC rules for naming compounds containing functional groups.

Solution: The following rules may be considered in naming compounds containing one functional group :

1. The name of a compound containing a single functional group is obtained by adding a ruflix to the root derived [rom the name of the hydrocarbon of longest carbon

chain. This Buflix replaces the ending -aae. (For suffixes of functional groups, Bee A Textbook of Organic Chemistry by DT. RK Bansal).

2. The chain is '110 numbered that the I\mctionw group always geta the lowest number.

S. A functional group containing a C-atom is always assigned position 1 and ita location is not mentioned while writing the name of the compound.

Esampler.

1~6

a 15

o

~

I 3 5

AAI

~ a eOOH

5 -Methylhex -Lene

(Jetter e is retained in terminal -ene because of it. terminnl position)

2·Penianone (Pent.2.one)

4·Methylpentanoic acid

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16

Organic Chemistry-Problems and Solution.

Ethyl 3,a·dimethylbutanoate

N,N·dimethylpropannmine (N,N.dimethyl. l-aminopropane is wrong)

2-Metbyl·s.bexanamine

H

4 21

5~N""" N·methyl-4-pentenom,ine

S I

Similar rules aa discussed above are also applicable for naming compounds containing two functional groups with some m0dific8tiona.

1. Out of the two functional groups present in, tho carbon chain in a compound. one is chosen U the principal functional group and it is assigned the lowerl number.

(For priority of functionw groups see, A Textbook of Organic Chemistry by Dr. RK. Bansal).

2, The name of the oompound ends with the suffix of the prinelpal functional group.

All other groupg pregent, are used as 'prelll<es.

~OH

3 I

t 2 1

5~COOH OH

Eumples:

o

5~~N

a

6~J

2 4 6

1~ 3 ~

(-en in -mternal poaition]

2-Methy 1-3-oxob umnal

4· Ketopentan.enitrile

I-Hexene-b-yne (6.He:<en.t.yne is wrong)

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Nomenclature 01 Organic Compounds

17

N oto tho difl'e.rence in the above two structures, The carbon chaio is numbered eoDllidering C-C as the, principal group. In contrast, if there is a choice for numbering (as in the seccnd structure) then C=C gets the preference over C""'Cbut the eompound is still named as alkenyne.

3,7-Dimethyl·6-<<ten·l-01

Problem 2.4:

Wri til IUP AC names for the following Htructures:

./'.._ /COOH (d) HOOC ..... <»:

if)~

o II

(g) CH.C-CCH=CHCH=CH. (h) CHI=CHCHPH (i) CHI=CHC~CCH3

o eHO

vlHOCH2CR,.0H (k)(CH,J,C-CHCHO (l)NH.CH.CH.~OCH. (m)~

-II .

Cl Cl

(n) CHaCH=C .. COOC,H, (0) H2NCOCH1CHCHCONH. (p) Ii:!C-CHCH2Br

I . I I

CHa CJ Cl

O~ /NH. ~C

(q)~L

~ 9H3

(r) HCCR.CCOQC"H,

I "c

CHI

A\, /Cl

C

I

(u) CH3CHCH •. COOH

(8) CH,C=CHCHO "I

CN

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18

Ofllllnic Chemistl')l-f>robIems and Solutions

o 0

II II

(w) CH.CCK,CCH.

~OH~

~) I (y) ./ ) I

~)y

/N"",

Solution, (a) S-Methylhex-l-en-5-yne (b) a·Cydopentyl-2.4-<iimethylpentane (e) :J-Methylpentanamide (d) 1,4·Butanedioie acid (e) N,N,a·trimetbylbutanamide (fJ l,4'Pentruiiyne (g) 2,s.:Heptadien-2-yne (h) Prcpen-f-ol (i) 4-Penten-2-one (j) 1,2-Ethanediol (10) 2,3-Dichloro- 3-methylbutanol (j) Methyl3-aminopropanoate (m) 2-Methylpentanol (n) Ethyl 2-methylbutenoate (0) 2,3-Dlchloro-l,li-dipentanamidc (p) 3-Bromo-l-propene (q) 3-Ca:rbamoylhelWloyl chlorid.8 (T) Ethyl 2,2-dirnethyI4-oxQbutanoate (,j 2-Methyl-4-0xlibutenonitrile (t) 7-Ethyl- 2,3,4,6-tetramethyldeeaci,8-diene (a) 3-ChlorofoI'IIIYlbutanoic acid (vl 3-Cyanopropanoic add (w) 2,4-Pcntanedione ttl 5-Methyl-6-octyn-l-<BI. (y) :J-Ethyl-5,7-dimethyl-5-propyloct-a-cne (2) 2,4,N,N-tetramethyl·a.pentanamine.

Problem 2.5:

Write the structures as well RII the correct namee fur the following compounds:

(a) 2-Pentyn-l-ene (h) 2-Allybutanal (e) 3·Cbloro-l,3-butadlene «l) 5·Ethyl-3·methyi· heptane (e) a-Butene (j 1 a,a·Dimetbyl-l·propyne (g) 1,a·Pentyne (II) Vinylacetic add (i) 3-OJ:o·7-oc1ano1 ('0 H",,·2-en-6-01 (h) :J-Buten·l-yne (I) 2·Methyl propyl ethnnoate.

Solution: (a) (2.Pentyn.4.ene) (6) (2.Etbylpentnnal) (e) 2·Chloro-l,3-butadiene

~ ~CHO (CH.=C----CH=CH._)

. I

Cl

(d) a.EthyI.5.metbylheptane

~

(e) L-Butene (CH~=CH-CH!-CH,J

if) a;Methyl.l.butyne (CH-C----CHCH,) I

CH.

(g) 1,S.Pantadiyne (HC-e-C-e-CH,)

[h) 3·Butenoic acid ~COOH

m l·Hydroxy·5-heptanone o

~CHOH I

{Ji Hex-4-en-l-01 (CH"cH.=GH-C~--CHr-CH20H)

(k) I-Buten·g·yne (CH2=CH--C-CH)

(l) 2.Methylpropyl ethanoate

o CH.

II I

(CH~-e--o-CK,-CH-CHJ

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NomencialUre or Organlc Compounds

19

Problem 2.6:

Define, a functional group. Nama soma surlt groups, containing an O%)'gen atom.

Solution: A/Unctionalgro14p is defined as the chemically reactive part of a molecule. El<ample8 of some functional grouP" containing IUYgen atom are:

-COOH (Carboxyl) '()H (Hydroxy) -CHO (Aldelzyde) -CO~ (Amide).

Problem, 2.7,

Can bomologuee be isomen?

Solution: No, because homologues do not have the same moleeular formula. They differ ftum one another by the possession of an additiOlUll eR:! group. Ho=logues though have oimiIar chemical properties.

Problem 2.6,

Write a IItrucl.ure CQrresponding to the following names:

(a) 2,7- Dimethyl-3,3-dichlor0-4-sec- buty 1-4-i sopropy I-li-n -buty 1-6-chloromethy 1- 7- bromononane. (b) 2-Butyl-4-hydrolQ'-3,N,N-trimethyl-2,fj..heptadien-l-amine. (c) 2-Methyl-4- oxo-2;butenonitrile,. (d) Methyl methyl propanedioate, (e) 2,N,N-trimethyl-3-ethoxypropanamlde.

Solution: (al

OH

(b)

7

(d) H.COOC~ COOCH~

hoblem 2.9:

Select the correct answer from the following:

(., TIre !UPAC nama of' O. (.

A. 2-Phenylbutane

D. 3·CyclohelQ'lbutane

B. 3-Phe~lbutane

C. 2-CydohelQ'1butane

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20

CH.

31 2 I

(h) The IUPAG name of CH,-N-C--CH:r-CHa ' i.

I I. 0 CH, GH.CH,

A. 3·Diml!thylo.mine·3·methyipentllrre B. 3,N,N-dimethylamino-3-ethylbutane

C. 3.,N,N-trimethyl-3-pentemamine D. 3-DimethyI8.!!li.n0-3~thylbutane

(e) The fUPAC name of ~, is

A. 6,6-Diethyl-8-methyl~7-decene B. 5,6-Diethyl-S-Dlethyldec-4-ene

C. 3-Methyl~,6-diethyl-O-deeene D. 5,6-Diethyl-8-methyl-O-dccene

(d) The fUPAC name of CH2 -CH-CH2, is

I I I

CN CN CN

A. 1,2,3-Trioyanopropanedinitrile B. 3..cyano-l,5-dinitrile

C. Propanetricarby lamine

O. 3-Cynnopentan-l,5-di.nitrile

(~) The WPAC name of CHa - C= C - CHa ' is

I I

C2H6 C2H6

B. 1,1·Dietbylbutene

A. 3,4-Dilnethylhex-3-ene C. 2-Ethyl-3-methylpentene

(/) The structure of 4-metbylpent-2-cne, ;8

CH3, A.C=CHCH CH

CH,/ .,

D. 2,4-Diethyl-2-hutene

(g) Th.e WPACneme of CHa--..c~N, is

A. Acetonitrile B. Ethanenitrile C. Cynnoethane D. Methyl cyanide

Solution, (a) C (b) C (e) B (d) 0 (e) A if) C fg) B.

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I CHAPTER I

3

Factors AffeCting Acid Base Strengths

Problem 3.1:

Write short notes on the following:

Solvation, resonance energy, electrophilcs, nueleophijes, Lewis ac:ids,tautomeri$!D, resonance hybrid, inductive effect and steric effect.

SolutioruSolvation:A solvent direcl.Iy interaets with the dissolved ion. The ion is surrounded by the sclvent meleeules fanning the solvati.on shell. This process is cal.led..,/vation. The solvents affect the stabilities of ione in many cases. For example, polar protie 6(.1 vents such as water and alcohols are capable nf effed:lvely .solvating both cations and aninns. CatiOl'Ls are solvated by dipolar intaractions with lone pairs and the anions are solvated by hydrogen bonding. Polar aprotic solvents sueh 88 dimethyloolfoxide and dimethyl formamide solvate cations but do not effectively solvate anion s, ThWl anions tend to be more reactive in polar aprotie solvents.

Reeo.DIlDce Eaergy: The extra stabilization provided by the delocalization of eleetrons compa.red to a aon-defoealised ,structure is termed as ,..,SOlUl""" energy.

Electropbil8ll' Eledrophi1e8 are species capable of accepting eleetrons, Lewis acids are frequently called, electrophiles. An electrophile tend to attack a site of high electron density.

Nucleopblles: Nucle!Jphill!3 an! species capable nfdooatingeiectron" for bond fornrntion.

Lewis base" are, called nueleophile a.

Lewis Acidil: Species that are 8 hart of an electronic oc:tet by one or more electron pairs are called Lewis acU:1s.

Tautomerism: The rapid equilibrium between two i90m e ric functional groups is called tautomerism,

Resonance Hybrid: 'The actusl structure of a molecule is considered to be a ,""",.na"ce hybrid of all the possible Lewis structures which are referred to as contributing structures or

cannnleal structures. For benzene the eanonieal forms are 0 ............ 0 and is a Bingle compound that is the average of both the se structures. Benzene ie tho!! a hybrid ofth ese structures and is "represented by ©.

21

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22

O'll8l1ic Chemistry-f'roblems and Soiutlons

Inductive, 'Effect: In tbe case of resonance effect the electrons are transmitted through an alternating system of single, and double bonds. There is yet, another way of electro';,i. displacement and it takes place through a saturated earbon chain when an electnm-donating or electren-withdrawmg group is present, on the chain. This is called the inductive effect and it is (I polarlzntionthrough a sigma bond. Moat clements that are substituted, for hydrogen in organic molecules are more electronegative than hydrogen. Therefore, IIlOSt auhatituenta such 88 -N02, -Nli:z, -OR and halogens exert electron-withdrawing inductive effecta. ,For this reason ehlorcaeetic acid is stronger than acetic acid. This effect falls off with distance from the suhlrtituent.

Sterle EJI'~ An ene.rgetically unfavorable effect on any physical or chemical property that results from van dar Waals repulsion is termed<18tern effect. Thus when it is said that the energy harrier to rotation in butane is more than that of ethane, it is because there are two metbyl groups in butane which interfere with the rotation. Sterie effecta are caused by mteractlens between atoms Or groups that are non-bonded to each other. In other words it results from the presence of bulky groups.

From the K. values of the following phenols, it is obvious that (C) has the lowest acidity.

The reduced acidity is attri,buted to stene effects. In order for resonance interaction to operate between the substituent and th,e ring, tho substituent, muet lie in the plane eftbc ring. Such a geometry is not available for phenol (C) because of the presence of two arrha methyl groups. As a result the nitro group ispusbed out of the plane of the ring and effective deloca.lUation of tho resultant phenoxide ion doee not take place, This effect is also termed as steric inhibiti.", to re'Ollo1lCe.

NO. (a)

'Ka 700 ~ 10 _,.

CH,*O.H ca

--3 . ::I.

VI

;:,._

NO. (b)

700" 10-10

CH'~CH'

NO, (c)

_ _-tt

60><,10

Problem 8.2:

PrOOict, the relative acidity of the following pairs:

(0) Ha0' and NH/ (b) CHaNli:z and CHaDH

Solution: We examine the coniugate base being formed when each acid loses ... proton; tho better the coQjugate base accon:unodates the electron pair left; behind, the weaker the base and hence stronger th.e acid.

{oj ~O· > NH/

o...ygell is more electronegative than nitrogen and can hold on to electrons better. Therefore. HaO' ... ill tend to lose tbeproton more rapidly and more acidic.

(b) CH"QH > CHoNH"

Again because ozygen is more e\ec:tronegath ... than nitrogen, CRaOR i8 more acidic.

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23

Problem. S.8,

Draw the resonance contributing 8tructu"", of the following molecules: o 0

II - II o-~

(a) CH,C--Y-CCHa (6) CHaN02 (e) f _ 0- (d) CH3C~CH=CHN02

H

o

II (e)CHsC~

CH.~.

if) I CH. (a free radical).

CH,

Solution,

-

-

'0' '0'-

CII(? I +

(e) CH~NH~ - CH,-C=N~

Problem SA:

. (a) Which is more acidic and why?

COOH

(rC]

:0'

<:6

o

if) CH"~ rJJ- . CH3~

'Y'CH.- I ·CH.

CH. CH.

Of

COOH

¢

Cl

(6) WhiCh is more basic and why?

H2NCH,COO- Dr H:>,~CH~COOH3

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24

Organ'ic Chemistry-PrOblems and Solutions

SolutIOD: (a.)

>

CI

pK. 1.94 3.99

Because of the l!I.I"g\'r inductive elettron-wlthdrawin_g effect of Cl in the ortiJo position, the negative charge on the carboxylate ron is stabilized, after the I""" of a proton.

° 0

.•.. II . ...... II _

(b) H.NCH.COCH. > H;NCH2C---O

Because of the greater inductive electron-withdrawing effect oftha carboxylate ion, the electron dCtlsity on the nitrogen. atom ia decreased,

Problem 3.5:

(a) Would BrCHC~COOH be alltronger acid than Bl"C~CH2COOH ? Why?

I

Br

(b) Why is the compound (CF.>aN virtually uon-basie ?

Solution: (oj Yes, because the two j}-Br groups are more effective in .stabilizing the carboxYlate ion inductively. (b) The trifluo.romethyl groups withdraw electrons inductively making the electron pair on the N -atom virtually non-available for donation.

Problem 3.6:

(0) Write the following in the increasing order of acid mength: o

.. II

CCI3COOB, NBs, BCOOB, CH3COOH, CHsC~, CFsCOOH (b) Write the following in the decreaaing order o.r base 6tn!ngth:

C.H.~B., :Qlf. NB" NB.- , (CH:J;NH, CHi?H. CH3NR.

Solution: (a) NHa < CHaCONH, < CHsCOOH < HCOOH < CClsCOOH < CFsCOOR (b) NH-.- > OH- > (CHa);Nfi > C~ > NBs > CJlr;~ > CHa0R Problem. 3.7:

2,4,S-Trinitrotoluene is a relatively acidic compound. Explain why the proton is easily removed from the methyl group?

Solutiol1:

0",. CR,. olJ Rs._H, -0 . CH,

N*V NO, 0o", %1!~NO' \VN02

0/ 1--" -0/ I -- -0/ I - etc.

"'- - "'- "'-

NO. NO. NO.

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Faclors AKec1ing .Acid Base Strengths

25

ThOproOOD is removed ~y because the anion formed after the removal of the proton is stabilized by resonance with the th ...... -'NOz groups as shown above,

PrOblem $,8:

(a) State Lewis concept of acids and bases, (b) Can a proton (H+) be regarded as an acid according to Bronsted and Lowis definitions ?

Solution: (a) Lewis acids are specie. that can accept a pair electrons, and those which donate are LewiS bases, (b) H+ is not a. Bro.llIlted acid but is a Lewis acid because it can accept a pair of electrons.

Problem 3,9>

(al The heat of hydrogenation of t-butene is 30,3 Kcallmole and that of 1,3-butadiene is 57.1 Kcallmole .. Calculate the resonance energy ofl.3-butadiene. (b) Can z.-butene be chosen

as a model instead Olf l-butene in the above ease ? .

• . . Catalyst

Solution: (a) l-Butane + H. _ Butane + 30.3 KcaVmole

. Catalyst.

1,a.Butndiene + 2H. _ Butane + 57.1 Keal/mole

I,S-Butadiene might be expected to evolve twice the heat of I-butene

(2 x 30.3 .. 60.6 Kcallmole). Therefore, tho difforonco 60.!> - 57.1 ~ 3.5 KcnJ/rnole is the resonance energy Olf 1,3-butadiene.

(b) No, because z.-butene· has a lower heat of hydrogenation (28 KcalIInole) due to its own stability.

Problem S.lO:

Classify the following into Lewis acids, bases or neither:

HF, BF~, HC ee CH, NOt, CH$CN, H20, CHaOH, C,He, At: , SnCl~, 1-

SoI"tion: Acids: .BF ~ , N02 + , Nt' Neither: HC-CH, C.Hs. HF Problem 3.11:

Arrange the following in decreasing order of acidity:

phenol, p-cresol and p·nitruphenol. Givereasons for your answer.

Solution: p-Nitropbenol > phenol > p..:resol

The nitro group is electrcn-withdrawing and stabilizes the phenoxide ion after the 10"" oca proton, while the -CH3 group is electron-roleasing and makes the phe:noxide ion unstable.

Problem 3.12:

Trifluoroethanol is 1000 times more acidic than ethanol. Explain.

Solution: Because Qf the presence of three strong electronegative nuorine groups, the release Qfproton is facilitated or the trit1uorootltOl!:ide ion isinduetively stabllized.

Problem 3.13:

Neith.er pure HzS04 nor pure HCIO~ conduct an electric current. Explain, Sol"tion: None of the two acids is icnieed in the pure form.

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26

OrganiC Chemisfry-Problems and SolutiOns

Problem 3.14,

(a) Which is a strongest acid and .. hy ?

CICHFH:!CH2COOH, CHaCli:!iHCOOH. CHsCH2Cli:!CQOH, CHsTHCH:!COOH

CI CI

(b) Which is a strongest billie and why?

CHaN-ii:!, NRs, CHsCli:!Cli:!NIi:!, CHaCH2NH2

Solution: (a) Clf"CH"CHCOOH is the strongest acid because the electron-withdrawing CI

I .

Cl

group ie nearer to tho carboxyl group. (b) Propylamine because tho propyl group is a better electron donor than other alkyl groups.

Problem 3.15,

Write resonance contnDuting structures for the following molecules:

-

H :0:-

<, C/··

cO

and

----

-o ....... l;:o -0 <: /0- -0 <, +/0- -0 <s.: 0-
N N N
0 ~O 6~· 6+
0..1 ---- ---- ----
..
~H' .. + +
'QCHa :OCH., 6~
co 6~
VI - ---- ----
0..
(J U
Problem aut, Solution:

Write an expression for the acidity constant (K,,) of benzoic acid and shew that pI{" is equal to the pH of a ha!f-io.ni~ed aqueoue solution.

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Factors AlI9Cting Acid Base Stnmglhs

27

K" ~ [C§H5COO-][H~O·]

. [CGH~COOH]

If the acid is halfionized, then [C6f4COOHJ~ {Ce~COO-]. In t:Iili! CW!e 1<.. ~ H,O"" or pH - pK"

Problem 3,17:

Label the msJor and minor contributors in th .. following seta of resonance structures:

o O-

Il I

(b) -CHr-C-CH3 - CH,=C-CH.

A B

+;0- +,0

(a) CH.=N· -CH=N

. '0' 2 '0·

A B

0- 0

I II

(e) CH,C=CH-C-CH, __

A

o 0

II _ II

CHg-C-CH-C--CH.

B

0-

I (")HTNH2-

A

(d) CH:rCH=C=W - CHg-CH-C-N

A B

Solution: (a) A (b) B (c) A (d) A (e) B

Problem 3.18:

The K,. of acetic acid is 1.2 " 11)-6 and the pK" of phenylacetic addis 4.31.

CH,COOH CsHsCH2COOH

K. 1.2" 10-' p K" 4.81

Calculate the pK" of acetic acid and K" of phenylacetic acid. Which of the two acids is stronger? Explain.

Solution:

CH3COOH x.. 1.2" 10-'

pK" - -Jog K"

C6Ht;CHaCOOH pKa ,4.31

Substitute the values to obtain PI<.. and I<..

PI<.. 4.76 K" 5.1" lO-li

Phenylacetic acid is stronger because of the inductive electron-withdrawing effect of the phenyl group.

hoblem 3.19:

Arrange the following aminea in the order of their decreasing baSicity .. Justi.fy your lII18Wer.

(I)

(2)

(~l

(5)

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28

Qryanic: Chemislty-Problem$ and &4u1ions

Solution: 3 > 5 > 1 > 4 > 2

In (3) the resonance, of the electron pair on the nitrogen atom is hindered by the two orth» methyl groups. In (l) and (4) there is more electron deJUlity on the nitrogen atom. In (2), which iI! least basic, there is exteumve resonance of the electron pair with the ring.

Problem 3.20:

Arrange the following acids in the order of decreasing acidity. Gi va reasons for your

answer.

H-F,

H-1, HBr

Solution:

>

HI

H-Cl

and

H-Br HF.

>

HCl

>

Ka 6.0 ~ 10.0 2.2 • 10'· IJI M 10" 1.8 " 10""

As the size of the halo atom ;JlCreIlHeB the bond length of hydron halide increases. The larger tIl.e bond, the weaker it is. Hence the hydrogen can be easily removed. m having a larger bond length than others is the strongest acid. HF, on the other hand, has a high bond energy. Moreover, because of strong H-hood formation in HF, the H-atom is not easily ionized.

Problem 3.21:

Name the tools for making QuaiitatiVll estimates ofstructuroi features thatmigilt eta.bili.z:e or destabilize the molecules with closely related structures.

Solution: At least the following four tools can be employed for this purpose:

(i ) The resonunce effect (ii) The Inductive effect

(iii) The sterie effect (tv) The hydrogen bonding elTeet.

Problem 3.22:

Triethylamine (a) gives no detectable adduet with trirnethylbornne whereas quinueltdine (b) forma a very stable adduct.

(a)

o

o

(b)

Solution: The ethyl groups shield the nitrogen atom of the amine to prevent any reaction of triethy lamina with trimethylborana. l!!. quinuclidine, in OO!!trast, the earbon al.(lIll!l are pinned at the back in. the ring system. Therefore, the nitrogen. aOOm is .free to attack tri.methylborane and hence' form a "table adduct.

Problem 3.23:

Write the formula for the col\lugete base of each. of the following Brdnsted acids.

(a) (CHs)aC· (b) ~SO~ (e) CH4 (a) C:JI50H2+

CH

Solution: (a) , __ ~;C=Cfit (b) HSO' (e) CHij (d) C2~OH CH.

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Fao;tors AllectJng Add Basa SImngths

29

Problem 3~

What are super scids?

Solution: Super acid.! are mixture orfluorosulfomc acid and antimony pentalluoride (FSOaHSbF 6)' Such mixtures are U8I.Ially soluble in 802. and are among the stron~t acid so lution known. Alkyl cations can be kept Indefinitely in stable form in super acids.

Problem 3.24:

Why ill phenol acidi~ ?

Solution: Phenols, like alcohols can ionize.

OH

6 +H,O

Phenola are considerably more acidic than alcohols or similar size and shape. Phenol, for instance, is 10' times more acidic than cyclohexanol. The enhanced acidity of phenol is due to the stabilization ofita conjugate base anion. The anion is stabilized by resonance, and the negative charge is spread over ring C·atolllll.

Problem 3.211:

What are the two ways by which the following cation can be stabilized.

CHa"-C/CH3

I

en,

Solution: 'The tertiary butyl earboeanon may be stabilized by electron inductive effect. In this case the -CH3 group being an electron donor, decreases the positive charge on the central carbon. atom and thus :increasos its stability.

A se<Xlnd factor that aeceunts fur its stabilization is hypetconjugation. This involves the overlap of bonding electrons from tho adj aeent (I bonds with the unoccupied 2p orbital of the earbceaticn, This is depicted as follows:

Sim_ilar structures are possible for a C-H bond in each methyl group. More the hyperecnjugative structures, more stable ill the cation.

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30

Problem 3.28:

III trifluoracetic acid the strongest aliphatic acid ? What is its pK" ?

F I

Solution: F-C-COOH ia the strongest. acid because of thepowerful inductive electron-

I F

withdrawing effect of the three F groups. Its pK" is zero.

Problem 3.27:

.. +

Why i. the structure R-C-O:, is more stable than R-C=O for the acylium ion .,

+

SoIuthm: In the structure R-C-O: , each atom has complete octst and most of the positive

..

charge resides on oxygen. While in .R-C=O, the structure of the acylium ion usually written, tho carbo.!!. atom has only six electrons, i.e. two short of octet.

Problem 3.28:

Wou.!d yon eYpeCt the inductive effect to be dependent between two centres,

Solution: Yes. The e!rect decreasea if the distance is increased.

Problem 3.29:

Describe the weighted average strueture of II. molecule.

Solution: If two resonance structures (unlike in benzene) are not identical then the molecule may represent o. weighted average of the two. 'Thi. impUer. that one of the structures i. more important than the other in describing th.e molecule. For example, methollymethyl cati.on can he written 118:

CHr4--cHa - CH2=Q-cHa

The structure on the right is 0 better description of this cation because all atoms have complete octets. The C-O bond haa significant double bond eharaeter and moat of the positive charge resides on the oxygen.

Problem 3.30:

Dmw resonance contributing structures of:

.'¢

NO,

o.J 001:.

Solution: {aJ ~V -

N· 09- ......_O~

(b)~

OH

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81

-

~-

+OH

Problen18.31:

Arrange the following acids in increuing order of acid strength and explain your SII&Wet'.

COOH
if COOH COOH
6 2
""""0
A B C
Solution! B<A<C Occurrence of H-bond in (A) makes the \088 of a proton difficult. Henee it is less acidic tban(C).

Problem 3.32:

Which has a greater acidity, D or CH3-CHr-CHa?

Solution: Cyclopropane, the C-H bonds in it have mote S character, More the s-ebaraeter, greater is the acidity and lower the basicity.

Problem 3.8&

Select the correct answer from the following:

(0.) Which of the following acids has the lowest dissociati.oD conetant ?

A. CIfs?HCOOH B. BrC~C~COOH C. CH3?HCOOH

Br F

D. FCH9CH2COOH

(b) Which is the IllilfIt unlikely resonance structure ?

A ¢ B ¢ C ¢

N+ N+ N+

0'" ...... 0- -0...... '0- 0"'''''''0

(el Among the following whichbas the moot acidi.c a·H ?

o 0 0 0

II II IIII

A. CH3CC~CHO B. CH3CCH2CCH~ C. CH3CC~COOC~

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32

(d) The increasing order of acidity among phenOl, p.metlzylphenol, m·nitropheno[ and

. p·nitropheno\ is: .

OH OH OH
6 ¢ &
NO.
CH.
I II III
A. lII, IV, I, II B. IV, III, I, n C. II, I, III, IV (e) In the following compeunds the order of bllllicity is:

and

N02. IV

D. I, n, IV, Ill.

c

N

o

N I H

(0)

N

I H

IV

c. III > J > IV > IJ

o

I H

I

A. I)IV>lI>UI D. IV > I > In > II.

if) Resonance structures of a molecule should have:

A. Identical arrangement of atoms B. Identical bonding

C. Nearly the same onergy content D. Same number of paired olectren.s

11 III B. 1I > I > IV > m

and

Solution: (0) B, Br '" le~a electronogative than F. Be.!!idM the distance between Br and CooH is large, Ib) C, In this structure nitroiJen Is pentavalont. (e) B, the resultant anion haa four resonance structures. Id) B, -N02 group is a powerful electron"withdrawing group. Moreover, the P"nitro phenoxide Ion is also resonance stabilized. (e) A, I ill a saturated oompound, there ill no delocalization of nitrogen electron pair in the ring. In D, the o:s;ygen atom. ill elecironegative. Compound III is virtually non-basic, {fj B, C, read the rules ofn!8Onanoo.

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I CHAPTER. I

4

Stereochemistry

Problem 4.1:

Describe the following terms,

Stereochemietry, mirror image, option! activity. meSo compound, diastereniaomer; resolution, racemization, relative and absolute configurations. chiral center, conformation, gauche and anti conformation, sterecspeeifle reaction, enantiome:rs, Fischer projection and stereoisomera.

Sol"tion: Stereocbl,mistry' Chemical studies that take into account the three-dimensional 8.5peets of meleeules ;8 referred to as stereoehemistzy.

Mirror lmaae: The imago thot would be seen if an object. or a molecule were viewed in a mirror.

Optical Activity' The rotation of polarized light by ehiral molecules. One enantiomer must be present in excess of the other for optical activity 10 be observed.

Meso Compound: An optically inactive compound whose molecule" are aehiral even though they contain chiral centers,

Diutareoiorome'" Stereoisomere that are not anantlomers are called dia.9tereoisomers ..

The meso tartaric acid is diastereoisomer ofthe(d, i) enantlomers of the acid. Diastereeisomera contain two or more chiral carbon atoms.

Resol"tlon: The process by which a mixture of two enantiomers is separated. (resolved) into two individual optieal enantiomeric forms is called resolution.

Racemization, The process when an optically active reagent give. 8 product that show" naith e r reteneion of tho configuration nor in. version of configuratipn is called racemization.

Relative ConfilfW'8tion: Chemists have determined the absolute configuration of mony chlral compounds by x-ray crystelJogmphy since 1951. Before that, however. it WIlB possible to correlate the confi!,urntion of one compound with that of another and to show that the two compounds have the same OT opposite ronfigurations. For example, when We convert one compound into another using a reaction that does not atrect the bonds to the ehiral atom, we know that the product must have the Same relative configuration as the reactant. The relative conlilluration ;b then the experimentally determined relationship between the configurations of two molecules.

33

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34

Organic Chemistry-Problems and Solutions

Absolute Contiguratl.OD: During our study of stereochemistry we have dmwn threedimensional representations and the Fischer pl'QjectiOTUl, and also stated that the ehiral carbons have the R and S configuration. All these method!! or describing the configuration about a chiral atom are absolute, i.e. they give the aetual orientations of noolllll in spare. Therefore these methods specifY tha abBO/ut. con{iguroti,,,,.

Chiral Conter: An atom in e molecule that i& linked to fOUT different groups. Conformation: A spa.tial arrangement of the atoms of e molecule that can be converted into another arrangement by rotation around the 8ingle bonds.

GauChe COlnformation: In butane, for instance at 11 dihedral angle Olf 60", the molecule is staggered and. tIl.a methyl groups are tothe :right and left of each ether, Such a conformation with adihedral angle of 60" betWeen the IOrg\ll!t grouP" lit called the gauche conformation.

Anti ConformatioDS: For butane, there is another staggered eonformation in which tho two methyl groups are in oppoeim directiona. Therefore, a coofonnation with a dihedral lingle of 180" between the largest groups i& in ant. conkmnation: This is often the confo.nn ation with lowest ene.rgy.

Stereospecltlc Reaction: A reaction in which the stereochemistry of th.e reac.tllnts is retamed in the products is called a slerea'p«i{1C reaction.

Erlimtinmonl' Moleculea that are non-sujrerimposable mirror images are called enantiomers.

Fischer Projection: It is a method of writing two dimenaional structure of molecules containing chiral atoms. In the Filrcher projedion we imagine that the longeatehain containing the ehiral a.toms liea vertically in the plane of the paper in a. eonformati.on such that all group.! and. atoms are oriented hori~ontally in front .. fthe paper. The vertical chain is then represented by a Une and the groups are joined by CmMbaT8.

The conversion of lactic and tartaric acids into Fischer projection ill shown below:

CooH COOH
H,i/cOOH ~ H+OH
~
C ... H-C-OH -
HO ....... i "CR, i
q... ca, CH.
(-) - '.actie aeld Fischer p .... j octl"n
;2£oH H on COOH
OH ~ Hoy?'oH - H+OH
no . H
no COOK
COOH COOK Tartaric •. cid Fioehor projection

Stereo~meno: Isomers that have their atoma joined in the same order but differ in somo reepect of the.ir three-dimenetcnal structu.ree are called stereaiBOmer,. StereoiSQme.T8 are either enantiomers or dlaatereeisomers,

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Stereochemistry

35

Problem 4.2:

airel.e all asymmetric carbon atoms in the fGllowlng structures.

ca,

I CHOH

ArBr

(b) X""

H .. ''11 CH3

o

o

II II

(a) HOH2C-C-CHOH-CHOH-C-CH,OH

OH I

c

(d) HO <, C""'c"'*O

W

8'" I CHOH

I CH.!OH

o 0 1111 Solution: (a) CH,OH-b-@HOH-©HOR-C-CH.OH

CHJ OR Br (b)

H,N CR,

CRa H

(e) C~H~HCH:.

, H)(c\6H

Problem 4.3:

Are the following' molecules aaymmetrie ?

° )ly-CH.

(bll_)

Sob~tion: (a) No, because identical carbons are reached at each step in going around the ring and the Br atom is reached a.t the same time from both sldell. (b) No, OOOOl!B(! 00 asymmetric carbon atom is present in this molecule.

Problem 4.4:

State w hethe r the following molecules ere ehiral or aehrral.

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36

Organic Chemfstry-Problems ar>d Solutions

?Ha

(b) CH3CHiC~ H Br

A

(dlX

H CH,(CH,),OH

Solution: (a) A<ihiral (b) Chiral (e) Chiral (d) Chiral. Problem 4.5:

Which symmetry element is present in the following molecule.

H

(aICI#CI H

xH

-r..

Solution: _(a) The molecule has a center of symmetry. (b) 'The moleeuJe has a plane ohymmetry. Problem 4.8:

'The observed rotation is found to be 4 . .05' ooun.terclockwi.se when one of the enantiomers of Z-butanol is placed in a polarim.eter. The sample was prepared by d:i.s!lolvi_ng 6 g of (-).2- butanol to a total of 4.0 ml and placed in a 200 mm polarimeter tube. Calculate the specific rotation of this .2·butanol enantiomer.

Solution: Since it i. levorotatory, it must be (-).2-butanol. e", 6914.0 ml '" .0.15 gil l"2001D.IIl,,,2dm

..... ·6 . [r 4 . .05

me speer re rotation a ., -~ ..

D \.0. 16,,2}

=-13.5'

The specific rotation for the other cnantiomer of 2-butanol obviously would be + 19.5'.

Racemic (±)-2-hutanol would be a mixture of equal amounts oC( .. }.2-butanol and (-)..2-butanol.

Problem 4.7:

Would you expect. tartaric acid written below as D (+) or L (+) acid?

B~*~H

COOH

Solution, L (+)-tm1.aric acid because -OH group is on the left hand side,

Problem 4.8:

What would it imply if 0. mixture has an enantiomeric excess (00) of 40% ?

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Stereochemistry

37

Solution: Enantiomerie excess (ee) of the mixture" 40%

This means thnt(lOO-4O)% is a racemic mixture. The ennntiomeris thus [40 + 112 (60)] ,,70% or the ratio (If the isomers in the mixture 'is 70: 30, i.e. '7; 3.

Problem. 4..9:

Mark, identical structures (j[ any) in the following:

COOH OH

(a) H+OH (b) H+COOH

CH, GH,

H

(e)Ho+CHa

COOH

Solution: (b), (d) and (e) are identical structures. Work. out according to Fischer projection. Problem 4..10:

Draw three dimellJlionai fonnulll of the following structures:

COOH

! i

(a) HO-g-H

1

CR,

COOH

I

i

Solutio.D: (a.) HO- C-H

I

CH,

CH.OB

(b) H+OH ...

CHa

CU.OH I

)

H-C-OB

i

CHa

~H.CH"

,

H-C-CI

PmbleIll4.U:

From each of the following pairs of structures, indicate whether they are identical or enantiomeric.

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38

Organic Chemistry-Problems and SoIuIions

H B_r=+·CH_ " (al

H· - eH.

Br

and

CH+H

CH:----t-H

Br

H CH_,.=+BT (b)

CH, H

Br

and

H CH,+Br HTSr CH,

SolutiOD: (a) same Ib) enantiomerie Problem 4.12:

Draw NeWllUl.ll prQjection fon:nul.n for erythro- aDd threo-2-bl'Ol!!Obutane-3-d,indicated below in FisCher projection.

H+Br HTO

CH, erythro

and

H+Br D----t-H

CH, threo

Solution: (a)

CH, (o'H" Br CH

H+Br CH , HXEr H*Br

"TO -H..... 0 ' -- H'1( __ ""3 '" D~H

CH, CH, D/H

CR,

e..,.thro

Fiecher projection La first eonverted into the sawhorse representation. To do this the bottom ehiral Carbon is written at the front and the top at the rear as implied in Fischer fonnula. The resulting structure i! a direct translation of Fischer representation. The front carbon in this strueture is now rotated 180" clockwise to give another sawhorae fonnula. Now convene;on ofthiB form into Newman proj""tion is eiUQ'.

CR, (blH+Br_

°TH

CH,

thrM

H)CB .• O.,(H"'" _ en,

Proceed in the some manner as in (0).

Problem. 4.13:

IndiCII.1.e whether the following pairs of compounds are:

(i) Two different structurea of the same molecule. (ii) Enant.iomers (iii) Different compounds (iv) Diastereoisome ...

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stereoome mlslry

a9

(b)

H+OH H+OH CH3

and

Br Id)HOOC~COOH and Ii

Br HOOC~COOH

\Y

H

C,H. CH,

H*C'H' CI*CH2CH2CHS

(~)' lind

Cl H H H

H H

Solution: (a) Bnantiomers, t:hey lire mirror images.

H.C H~H

X CA,

(b)HO H

-

HAH

HyOH .... nJ CH,

-

HO+H HO+H

CH3

Dhl!itereoisomers

(e) Enauncmers (d) Can be easily !lItat.ed, diastereoisomera (e) Drawings of the same molecule (f) Different compounds, not isomers.

Problem 4.14:

Draw thestructures of three nl<l$O dlastereclsomers of CSH12Br2.

Sol utiom M ""0 struct ures have a pl nne of sym m elry

H+'Br H+Br

C,H.

CR.Sr

H+CH.

H+CH.

CH2Br

:±!'

H+Br

CH.

40

Problem 4.15=

Organic: Chemislry----Pmblems ond SOlutJonS

Determine the RIB configuration of each chiral carbon.

CH. H

I I,Br

(a)......,C (1)) C"'"

HO/ 'CH,CH, . CHi' 'Cl

H

CH.(e)

I .

Solution= (a) (a) HO .?~' CH.CH,(b) (d)H :

¢

Priority of the groups is C C

1 I

(a) -C-CH2

1

CH,

Problem 4.16:

Cd);' :(;H

CHafe) I~H(d)

. ../0,

(b) CHaCH2 OR(a)

(R)

H(d) (e)CH" ... ,!..,,,-C!(b)

1

Br(a)

(S)

(a)lCl,

. (e)CH,,-Cy Ii(d) Cl(b)

H C C

I I 1

(b) -C-C-C

I I 1

H H CHa

(S)

(d)(b)~l(c) ~'H(d) (R)

H C

I. 1

(c)-C-C

1 1

H H

(d)-H

Arrange the fellowing' groups in order of inerelllli.rlg priority.

(a) -CH=C~, -C( CH')3' -CH3~CH2c(CH3)' (b)-COOCHa ,-COOH, ...{;H(OCH3) (cJ-C(CHa)2' -CH(CH3)z'-CHP

CHa

1 Sohltion: (a) a. -C -CBa 1

CH,

C C

1 I

h. -C -CH2

1 H

H H

I I

c. -c - C - CH2C(CH.).

I I ..

H H

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Ste'eochemlstry

41

(b) G.

o C I I

-C-O

I .

CHs

H

I

-C-Cl I

R

(el a.

o C I I

b. -C-O I

OR

CHa

I

b. -C-CR, I

CR,

OCR,

I

c. -C-OCR3

I

H

CRs

I

c. -C-CHa

I .

H

Problem 4.17:

Draw th.c cnantiomer,a of l,3·dichlorobutane and label them os (R) and (S).

ClCH2CR2CHCHs

I GI

I Z 3 •

CI- CR2 -CH2 -CR-CH,

I Cl

Solution,

The third carbon. of the compound is crural. None is needed to detennine the priority of the groupsltnked to the chiral carbon.

(")~CH.~CI (b) -Cl (e) -CRs and (d) -H

Based om the priority of the groups, the following mirrnr images are drown with the hyd.rogen atom being directly behind the chiral carbon. Thus the two enanucmers are the (ollowing:

(oIGR,CR,C)

I (cICHi"""" c-c, R(d)

'CJ(b)

(R)

(8)

Problem 4.18:

Draw the optically active and me.w form of 1,3-<:yclohl!X8ndicar~lic acid.

Sol."uru Hoo,d HOO,ri°H

~ U

optically active

Problem 4-1.9:

(a) Describe optical isomerism with suitable examples.

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42

Organic Chemilllry-P.,abiems and SoIutlons

(b) Would you expect the following compounds to be optically active? Explain.

H H

1 1

HOOC-C-C-COOH

1 1

Br Br

Solution: {a.) Optical isomertsm may be described as the existence of two or more nonsuperimposable mirror images of B compound leading to enantiomers, for instance, lactic acid, glyceraldehyde lind alanine.

HiH I :1

(b) HOOc--{;· .i, C-COOH

Iii

Bri Dr

One half of the molecule ia superimpoeable over the nlher. Therefure, the compound is not optically active but ""'50. Me8tJ compounds always contain two or more chiral atoms but aresymmetrica] molecules which do not give any net rotation of polarized light.

.Problem .4.20:

Indicate the possible types of isomerism exhibited by the following compounds_

(0) C6H!O (b) CHsC-<:CHs (c) (CHS)2C=CHCHs (d) C4H)Q (e) C1CH=CHCl if) CJlI) (gl CH3CH=CCIH~

I CHa

Solution: (a) Positional (Draw Structures) (b) None, (e) None (d) Positional (e) Geometric ifl Functional (Draw Structures) (g) Geometric

Problem 4.21:

Which of the following structures exhibit cis-trons-isomerism ?

( .. ) 2-Methyl-2-pentene (b) 8-Methyl-3-pentene (e) 1.2-Dimethylcyclohe:mne (d) Cyclahexeue (.) 2-Hexene

Solution: Firat dra w the atructures, then decide. (0) No (b) Yes (e) Yes (d) No (e) Yes

Problem 4.,22,

What type of isomers ia the following pair ?

H

H~ ... CH3.

H~H

CH.

Solution: These are conformers.

Confonners are molecules which differ from each other as a result of rotation about the c-c bond.

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Stereochemistry

43

Problem 4.23:

Write RIS IlOnfiguration (or the following compound!! :

(b) ~.

CH.-«H CH,

H

i

I

(a)CH.-C-NH,

- ,

t

• Solution:(a) CH'-'V-NH,

I

C.H,

O~CH'

(bJ (a) • (0)

CH, (b) ~ B(d) CH,

(8) COOH

{d)H'N+H CH,

CHO

(")"+08._CH.OH

H

H

- CH,+NH, ...

C,H,

-

(elCH.

I .

(c) (o)Br /C H(d)

\Cl{b) (S)

(b)COOH

1 (a)H,N-?'::-'CH.(c) -&i "'H(d)

(blCRO 1

(d)H .....-?~-CH,OH{C) --e: "'OH

(a)

H(d)

b~

(olCH[ \ C,H,(bl

NH.(a)

(a)NH,

I. ~~H(d) ...... C,

(01 CH, C,H.(bl

(B)

cooaei

1 __ -H{d)

(e)CH./C'NH.(a) (8)

CUO

1 .... H(d) (e) HOH.C-C <, OH{a)

(~)

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44

Organic Chemlstry--Problems and Solutions

Problem 4.24:

Show the relationship between the following pairs of compounds.

CH! OH H CH,OH

(a) H+OH and CH,+H (b) HO+CH.OH and HO+H

COOH COOH CHO CHO

Solution: (a) Make two changes of groups, an identical structure i8 obtained. (b) Make one change of groups, enantiomeric structure is obtained.

Problem 4.26:

(a)Q

How many optically active isomers are poa9ible for the following compounds ? CI I (b) CH~CH.CHCHCH3 I CH.

!yCB. __/\_

(~) y (d) Br~Br

Br

HO OH

Bf

Solution: The number of opticaUy active isomers is given by 2", where " is the number of

chlral centers. .

(a) 2 (b)" (c) 4 (r!) none (e) 2 if)2 (g) 2 (h) none (I) 2

Problem U6:

Indicate whether the following statementa are true for falee.

(a,) Rand S configuratioll8 eorreapcnd to the enantiomers of an optically active compound. (6) Thepreeeas of converting an optically active compound into a racemate is calledrecemiaation. (e) Cyclic diaubstituted compounds do not show geometric i.om.erism. (d) A molecule containing a plane of aymmetry can be optieaJ!y active. (e)Positionru and chain i~omeri&m are identical. if) Optical isom.ers that are not crumtiom.er.a are called diasterooisometa (gl Allorlilo substituted diphenyl compound. are optically active. (h) In the Fischer projection, any odd number of interchanges of substituents lead to an enantiomer. (i) All chil'al objects are eaymmetric.

Solution: (.,) T (b) T (c) F' (d) F (e) F if) T (g) F (II) T (il T

Problem 4.27:

By drawing Newman projection formula", show how do the potential energy ehanges occur in ,,·butane when th.e molecule is rotated. around its C2-C! bond axis through a complete cycle.

Sohltion: Conformation of IJ-Butane: Confonnationo are the result of fi:ee rotation about the carbon-carbon bond. In ethane the barrier to rotation is small and as a result the rotation about the carbon-carbon. axis is free. If one of the hydrogens in ethane is replaced by a bulq group, the barrier to rotation increases. In monoehlceeethane, for instance, it amOUll.ts to 3.6 KCallmole wbile in butane it rises to 5.5 Kcallmole.

l

U rheberrec htl lch gcsc h (jutes Iv! ateri"

Stereochemistry

45

I '2 3 4

CHs-CH2-CH2-CHs

The conformation of butane can be evolved in a manner similar to those of ethane.

As. in the case of ethane, the m,M unstable geometry of butane ill the fully etlipsed eonformatinn, a Newman projection (0) looking along the C2-CS bond ill shown. In this ease the two methyl groups are close to each other and 9 = 0'".

Hl)O' CH~6O'

]H3. H*CHa

H~H H H

H H

H

Fully ecii8ped (XI)

:~),w

CH. Anti (X1V)

O(luch~ (XII)

lH., ~~

~240'

Partially eclipsed OM

}H3\

~H)120'

H CH,

Partially ee\lp.ed (XlII)

CB,

c~*:

H 300'

G"U~M

Q(VI)

Most stable confonnation, however, i8 the staggered arrangement. But for butane there are two distinctive ~bilitie8: the methyl group may be orien,ted in opposite direction or may be in mud eloaer proximity. There are thus two minimum energy geometries which butane can adopt, and they are known as the anti 0011 9 = 180') the two methyl groups are trans. and gauche 001 and XVI, 9 = 50' and 300" respectively) conformations respectively. The remaining

etructurea (011) and (XV) are partially eclipsed. '

Figure below show" a graph of the torsional energy of butane as the moleeu\e ill rotated about the C2-C, bond..

t

XI

X111

120 1 eo 240 300

Angle, of rotation _

All the staggered conformations anti and gll,ucJw are lower in ene,rgy thno any of tho eclipsed ccnformaricns. The anti is more stable of the two gauche fOIms by about 0.9 Keel! mole, 'The difference between the forms is that the methyl groupe are closer togethe,r :in the gauc"" form. The two kinds of eclipsed fonn. have also different energies . .in the fully eclipsed form of higher energy, the methyl group. are very close together.

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46

Organic Chemlslrt-P roblems and SoIutIoos .

Problem. 4.28:

What do you understand by the tenJUI R end S used for apectzy;ng the configuration of an optically active compound? Do they throw any light on the direction of rotation of the

eempound ? - -

Solution: The only structural di_fference betweeuenanucmers is the configuration at the cl:liral center (or centers), The R-S system of nomenclature includes a way of denoting the oonfiguration at each chiral center, The configuration of any chtral center is named. WI R or S. The tenn .R (rectua Latin for right] andS (sinister, Latin fur left). TheR endS speeificatien has no 00llIU!Cti0n with the direction of rotation of polarized light.

Problem. 4.29:

«I) Is geometric isomerism possible in compounds which contain (i) Two double bonda (ii) No double bond? (b) Solutions of optically active compounds showing positive rotation are called dearo and the enes showing negati ve rotation are called leoo, Can these be denoted as D andL respectively? Give reasons fur your answer. (e) What is 'meso' form 1 How does it differ from racemic Conn ?

Solution: (a) (i) Yes, as in 1,3·bntadiena derivatives

6

CH3," 4/H /C=C,3 2/fl

H C=C 1

H/ 'CHa

tTanB, franil.2t 4--Rea.diene, (ii) Y (!II, as in cycloalkanes

CH,

dCH.

~H'

CH,

cis-I, 2-Dimetbyl"""loh".Iane ,,...,, ... 1, 2-Dim~hyl""cloheune

(b) The capitallette ... D and L refer to configuration and bear no relationahip with the sign of rotation. (e) A ""'60 fonn has a net rotation of zero, Le., optically inactive and is a diaetereotsomer of each of enanticmeric form of tho compound .. It cannot be resolved into its optically active components .. A racemic fonn also shows an overall rotation of zero but it can. be s~parated into its optical isomers,

Problem. 4.29:

Which ofthe· following compound. will eIhibi t optical isomerism ?

CH

(e) - ~)CHCOOCH.

CHa -

CHa .

(0) __ :::CHOH (b) CH3CHOHCOOH CHa

H

(e) SOVOR if)I(:FBr Solution: (b) and if), these are the only compounds which are chiraL

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Stereochemistry

47.

Problem 4.31:

Circle, all the ehiral carbon atoms with B circle in eholesternl and state the number of optical isomerll.

flO

Solution:

HO

No. "fisomers 2" = 158

Problem 4.32:

What is the relntioIll!hip betweell cis-l-<:hloro- ~nunrocyclohexane and ImJl8-I-chloro- 2-fli.lOrocyclohe"""" t

Solutiol>:

F

((CL

cu.l ... mer tnI .... l ... me.r

The two i9O!!\eT9 are diastereoisomers that, are not enBlltiomeric_ They differ in their three-dlmeneional structures but are not mirror images.

Problem. 4.3~h

Draw at leaat two Fiecher pl'Qjectlone of S-2-butanol.

1 2 3 i

Solution: CHa~CH--CH'l--CH3

I

OH

Carbon-2 is a ehiral center. The priority of grouP" is :

-OH -- 4JHaCH3 - 4JHa ---------- -H Therefore S-2-butanol is:

OH OR C,H,

H~c.~L'CH' --- CIH~+CH3 --- HO+CH.

@ H R

C,.H. -HO+H CR.

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48

Orgallic Chemistoy-Problems and Sotutions

Problem 4.34:.

From the list of fonnulaa below, select the one Or two which best fit each de.scription: (a) A cis stereoisomer (b) A pair of enantiomera (e) A ""'80 compound (d) Apair of diBllterooiBomer (e) A pair of compounds which might form a raeemle miKture

H-+08 H-+OH

HToH HToH

CR, CHO

Br-......C/CI II

H/C"CI

Br"C/CI

SolutloD:(a) II

H/C'-C1

H.,.O-+H._ (d)HoTH

CHa

H-f-.HOOH HOTH CH.

H-+OH (bIHToH

CHa

HO-+H HOTH CR,

and

HO-f-.HOH HOTH CH.

CHO (c)H+.' ., OH HTOH

CHO

CHO

and H~+~H (.)8.m ... (b).

CR,

Problem 4.85:

List three types of asymmetry shown by organic compounds,

Solution: Organic melecules may show asymmetry:

(i) If they poa8CSS a. chiral carbon atom (i,il Due to restricted retatien (iii) In allene derivatives.

Problem 4.36:

Distinguish D form d and L from I.

Solution: The symbols d and I pertain to the d:i:rootion of rotation in the polarimeter. But the capita) letters D and L refer to oonfigurati.on. Th..ey have nothing to do with romtinn.

Problem 4.371

Wh.en 4.0 g of an optically active compound. por 100 011 of solution was placed in a 20 em tube, the pi ane of polarized light. was rotated +5.8". Calculate the specific rotation.

U rhcberrec htl lch gesc h utztes M ateri a

Sle,,)pchem i$1 ry

49

a lxc

0=5.8°

I " 20 em or 2 decimeter c=41I00wml

. . Specific rotati.on" 2 ,,1>.:'04 '" 72.5°

Problem 4.38,

Write" fbrmula f"r" compound containing fourClU'bon atomB which should be capable of existence in 2" optically active forms.

Solution: 'rh" compound is 2"bromo-3·cb.!umbutmUl and it M" the following four enantiomers.

:::

Br+H

CIT" CHa

H+Br

CITR CHa

:::

Br+H

"TCI CH"

mirror

.eotmtiomers cnant_iQJncr8

\__ Dla.t4!reOl.om" ..... __) COIDPHI'll the molecule with tartaric acid.

Problem 4 • .19,

A 0.1 ·M solution of a compound (molecular weight 342) was placed in a one decim_eter !:ubean.d the plane of polarized light was rotated to +2.2'. Calculate the specific rotation of the

compound. _

Solution.:

B lxc

0"" + 2.2'

I = 1 decimeter

e '" 34.2 W1000 ml

.. 2.2 x 1000

.. Speeiflc rotation = ~ '" + 64.3

Problem 4..39:

Write all the stereclsomers ofthe following acid .:

CHsCH=CHCHCOOH I

CRa

CH H

(b) a -, C=C/

H/ "CACOOA

I

CRa

• .... H". /H

Solution: (0) /C=C"

CHa CRCOOH

I

en,

U rheberrec htl lch gesc h (jutes M ateri"

50

H

I C,

(c) CH,CH=CH/ \ CH~ COOH

H

I

(d) .... C,

. CH':/ CH=CHCH3

HOOC

Problem "'1:

Complete the folluwing structures by placing the missing substituentB in the correct positiona.

(a) s.G\ycerie acid (H~CBOHCOOH)

(b) S-A1nnine (CH3CHNH~COOH)

(c) S·3-<:hloro-l·butyne

(d) R·2-<:hlorobutane

OH Solution: (a) HOOO+C8,OH H

Problem '-'2:

(a) Whatia the hybridization ,ltBte of an wlene system? (b) How many lI,.(1rbita!s would be necessary in sa -II model oran allene ? What could be the relative orientation ob·on'bitals? (c) From YOIlT """wer in (b) what orientation of the terminal subatituente of the aliena would you, expect.

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Stereochemistry

51

Solution: (a) sr, 8p (b) Two oriented at right angle to each other. (e) Tho teJ"lninal aubati. tuents lie in a perpendicular plane.

ProblslIl 4.43!

Th.e a1lene 2,3-pentediene does not have a chiral carbon but is re.rolvable into enantiomern.

Draw an orbital picture that account for ita chirality.

SolutioD: The, aIIene has non planar chnracter. The two double bond systems in. 2,3'pentadieno are at right angle to each other. Due w this it hWl no plane of symmetry and its mirrer images are not 8uperimposable and tbiB allene is capable of !!.listen.,., in. (+) and (-) enanuemers,

CHa, /" ", /CH.

C=C=c C=C=C

H/ ,. GH' 'H

CHa 3

-

Mirror

CHa oo=o~:::~Q H

........ \U ,..,..,.

H-=C _', --' C----C

Q~::;:~~~CZJ:==::_-:O ........ CH.

In allene, the central carbon atom is 'P hybridized and linear while, the two terminal carbon atoms are sp2 hybridized and. trigonal. The two unhybridized p~rbitel.s on a 8p hybrid carbon atom are perpendicular. So the two ,,·bonds must also be perpendicular. Allene itself is ~hil"lll, however, .if somesuhstltuents are added to allene, the situatinn is different and it becomes chiral as in the case of2,S·pentedien.e.

Problem 4.44:

Compound A (C6"12) is optical)y active. On catalytic hydrogenation it gives optically inactive eompound CJlw IdentifY the structure of A.

BoIutio.n: Since compound A gains tw" hydrogen. aroma on hydrogenation, it must have a C=C bond. Therefore the structure of A is

H

CH3+CH!CH8 CH=CH.

Problem 4.45:

By drawing Newman projection,show how do potential energy changes occur in propane when the molecule is rotated around one of the C-C bond through II complete cycle.

SolutioD:The perspective and Newman projection of propane can be written WI follow. :

:t:

CH,

Peespeetjve d_l"awing

NeWD'lJlD projection

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52

OrganiC Chemistry-ProbIem$ and SoIutlon8

The following figures shows 0, graph of the torsional energy of propane Ill! the molecule is rotated around the C--C bond.

t i?

'" " '"

'" '_;l

1

III

II

3.3 k.callmole

II

1II

AIl in the ease of ethane and a-butane, the unstable geometry of propane is also ful!y eelipaed. This is shown by structures I and III in the Newman projection drawn by looking along one ofthe C-C bonds. In these structures a hydrogen and the methyl group are dose to eaeh other if e " 0 and 120". The torsional energy of eclipsed conformation is 3.3. KeaIImol more than that required fur ethane. Structure II is the stable staggered eoafnrmanon ..

Problem 4.4&

Write the favwed r:onfol"1!!ation (gaud1e, onti or eclipsed) for the following molec:ules.

(n) 1,2-Dkhloroethane (b) 1,2-Ethanediol (e) Propanaldehyde

CJ O_.....~

H.*H HH.·.*b_H'H

Solution: (0) _. (b)

H H

Cl H

anti

CH.

(e) . /'kP H~H

H

Gouela.!

(due kI H-bond formatlo.n)

Eclipsed

Problem 4.47:

Select the correct answer:

(0.) An enantiomerieally pure acid is treated with a racemic mbtture of an alcohol having one ehiral carbon. The ester formed will be

A. Optically active mizture B. Pure enantiomer C. Meso compound D. Racemic mixture

U rheberrcc htl lch gesc h (jutes Iv! ateri a

Sle reochemistly 53

(I» WhiCh of the following exhibit stereoisomeriem ?

A. 2.Methylbuten·t B. iJ...MethYlbutyn·l C. 3·Methylbutanoie odd

D. 2·Methylbutonoie acid

(e) The most stable confonnati<ln of ethslene gly~ol ia

A. Anti B. Gauche C. Partially eclipsed D. Fully eclipsed

'2 1 6

(d) In this organic compound l~. methyl group be attached to which

3 5 7

carbon to make it ehlral.

A. 1 B. 4

C. 3

D. 7

(E) How many optical isomers are there for butan·2.3-diol ?

A.. 1 B. 3 C. 2 D. 4

r.r) An important chemical method to resolve R racemic mixture makes nse of the formation of

A. Diastereotsomers B. Racemates C. A ""'so compound D. Enantiomers

(gl How many structural iMmers (ineluding seereeisomers) would be obtained by replacing one H of propene by chlorine ?

A. 2 B. 4 C, 3 D. 5

(h) Meso tortaric acid is optically inactive due to

A.Two aliymmetrie carbon atoms B. Molecular symmetry

C. External combination D. Molecular a.ymmetry

(I) The number of goornetrie isomers in the case of ehe following compound

~, are

A. 3

B. 2

C. 5

D. 4

(I) The correct statement about D, b, c is

: rei: : rH~: H~ rH~H

COO}! COOCH., COOCH.,

00 00 00

A. D and b are enanriomers B. a and b are identjcal

C. 0 and b are diaetereoisomera D. 0 and e lire enantiomers

(h) Which ofthe fo Uowing palm edtibit sterecisomeriam ?

A. Geometric isomerism and tautomerism

B. Geometri,c isomerism and optical isomerism

C. Geometric isomerism and positional isomerism

D. Optical i80meriBm and metamerism

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54

(1) Which of the fo!lowing i8 nat isomeric with diethyJ ether ?

A. Butan-l-ol B. Butanone C. 2-Methylpropan-2-oi

D. n-Propyb:n.eth_yJ ether.

(m) The number of geometric i!!On1ere for the compound with molecular formula CzStClFI is

A. 8

B. 4

C. 5

D. 6

SoIUti.OD: (a) A. this i8 the D;Ulst general method for the ItlllOlution of a racemicmixture, using an acid WI the I"e6I.llving agent, In this case the rocemic mixture is of an alcohol which is to be resolved.

(b) D, ~~-CB--COOH contains a chlral carbon.

I

CBa

(,)~ :y:

DB

In th.e anti form the two - OH groups are situated opposite to each other. (d) C, the C-<I will become ehtral,

H+CH~ OH

(e) C, .

HO .... H

CB~

and

HO+8 "TO" CHa

This diol has similar symmetrical structure WI tartaric acid.

if) A (g) D, CHaCH=CHC1. CHa9=CH~ , CICHzCH=CHa,

Cl

CH., /H CHa, /CJ

H/C=C,~, HjC=C'H

(h) B (i) D, two geometric isomers are obtained with each C=C bond. U) B, game structure one is written upside down. (k) D

(I) B, diethyl ether (C.Bu,o), butanone (C4HaO).

Dr,. /c! (m) D, /C=C,_ I F cis ... d , .... ""

Dr, /F Cl/C=C'I da and .l:ran&

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I CHAPTER I

5

Reaction Intermediates and Mechanisms

Problem 5.1:

What do you understand when We say a carbocation is stable ?

Solution: It implies that thoro is a delocalizatio!l of the po.sitive charge of the carbocation over other carbon atoms leadlng to il8 lower energy and hence il8 stsbility.

Problem 5.2:

Nitromethane is deprotonated in the presence of a strong base. Write the resonance structures of the resulting earbanion,

.i ,» Ba .... -8 ~o C\ +/0-

Solution: CH3-N ----- CH,,--.N - CH.~N '"""

"0- "0- '0-

Problem 5.3:

3,a.Dimethylpentsne is likely to form two radieals an treatment with a suitable reagent.

Indicate whieb radical would be mOTO stable 7

Solution:

CH,

I • (i)

CHaCH+ ...•. H,CH, J · CH'CH~H'CH'

CH. L rH,.

CH,CH.TCHCH, (2)

CH,

(B)

55

U rheberrec htl lch ge5c h utztes Iv! ateri a

56

O'ganic Cheml!llly-Pmblems and Solutions

The two radicals (A) and (B) will be formed.

Out of theee, (B) is asecondery (2.) radical and mo re stable.

Proble.m 5.41

What doe. a rate lawtell UB about the mechaniBm of a reaction ?

Solution: A rate law doea not. prove a proposed mechanism. But the rate law plays a role in ruling out BOrne meehanisms while leaving others as possible alternatives.

Problem 6.4:

Suggest a mechaniam for the following reaction.

,/"VCH.

L_JJ + H.O

+

DCI HCH, H' 0-" JCHCHa

rung

Solution: OH .- '.

-H,O ' .~pa ns !on

d ,/"VCH ~CH3~LJJ' -H

Problem 6.8:

Account for the following:

The species A, Band C are more stable than D, E and F respectively.

CHsCH=CHCHz', CHaCH=CHClt.-, CHaCH=CHCHi'

ABC

CH2=CHC":!CH2', CH2=CHCH2CHz,-, CH2=CRCHzCH2'

D E F

Solution: Species A, Blind C can be stabilized t7y resonance lind hence more stable. Problem 5.7:

Suggest II plausible mechaniam for each oUlIe following reactions :

OH OH

(blct-+

OH

(eleb

(-yCH. ~'CH3

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Reaction Intermediates and MeChanisms

57

'Ole

(h) eH", Ha

~NHOH •

s.;.llltion: (0) ~ ...!!..

ffNH,

I

::.....

HO

OH OH (b)(j-+

Pinacol- pinacolone rearrangement

CH, .hilt -H,O

r'r(CH,. r"t<CHa

(d) vCIICHacH .~CHCH.

I (1 •

OH ~H.

(irCH .••

~

H CH,

o=CH3

.

CH.

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58

Organic Chemislry-Problem. and SoIutJons

if) ~CHCH'OH HB,

phenyl migration -H.O

OiHCHrQ

Br

1.0

II (h)CH~H3

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Reaction t.ntennedtate. and Mechanisms

59

Closure

AQ 4=to

0-

~o

-

A tertiary alcohol will deh),<irat.. rapidJ.y

Problem 6.7:

The brnmination of acetone in the presen ee of Br2 and HBr has the rate law, rate = It [CI4COCHal [H"I. Suggest a mechanism for this reaction.

a

II HBr

CHaCCHa + Br2 -------- C~C~r + HBr

Solution: It is a second order reaetion. Both acetone and bromine are involved in the Blow step of the reaction.

aIJ::n

h' B_Br -... CH~-C=CH. -

-H

a II

CH~CCH,.Br + IfBr

Problem. 5.8,

Arrange the following cations in the increasing order of stability:

(CaB.)aC+, (CFa)s·, (CHa)sc+, (CCJa)3C', (CI4)2C~5G'

Solution.: (CFa)ac+ < (CCI3V' < (CHa)3c+ < (C14\C6.H6C~ < (C6Hs)aC'

Problem 5.9:

Separate the following species into eleetrophiles and nucleophiles:

CHaOH, 803, N02', MH, H~, NHs• OH-, HaO', Br

Solution: Eleetrophiles: 80s, N02,', H"O+, Br

Nueleophiles : CHaOR, RSIl, NHa, OR-, R28

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60

Problem 5.10:

Sketch potential energy dillgTllln8 for the following relll:tion~ and label E. and M{O : (a) CH. + CI' _ CHs' + HCI

'llili! reaction has an activation energy of + 4 KcaIImole and ~ of + 1 KcalIrnole. (b) CHs' + Cl:z - CHsCI + Cl'

The activation energy is + 1 KcaIImole and the MI' value of the reaeticn is - 26 KcaV mole.

Solutloa: (a) Since 4H' is positive, it is an endothermic reaction. The E. is higher than .4H' because the il8th £roll! reactants to producU! is from lower to higher enerior.

t ! I

R8attkx'I coordinate --------. (a)

(b) It is an ""othermic reaction.

I70blem 3.11'

1

f

I

,

.. t. .

E, ~ , ~caVmoIe

. - i . .l.

~+~ l'

Arrnnge the foDowing carbeeatlens in order of increasing stability.

(0)

(b)

(e)

(d)

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Reaction Intermediates and Mechanisms

61

Solution: The order of increasing :stability is the following: a<b<~<d Oarbeeation (a) is least stable because it is primary.

Problem 5.12:

Optio:eUy active. CH$ClI:lCH( OH)cHa was found to have lost its optical activity after standing in water containing a few drops of acid. ExPlain.

Solution: Addition of acid protonates the alcohol, Protonated alcohol subeequently eliminates water to form a carboeation. The resulting earboeation CIIJl either undergo rearrangement or elimination to yield an opticaUy inactive product.

CH3CHt~HCH3 + H+ . CHaCH!9CHfl

OH OH~

-

-H,O

CH:r-CH=CH-CHa Optically Inactive

Problem 5.13:

Define kinetic control and thermodynamic control of chemical reactions. Illustrate with a pertinent example.

Solution: In certain reactione the less stabte product is formed r""tor thlln the one thBt ill more stable. For instance, in the BBr addition. to l,a·butadiene, the leu stable l,2·additiOD productie formed ingreater amnunt ill hydrogen halide addition, provided the addition products are isolated before they CIIJl rome to equilibrium. The formation of less stable product is governed by l<indiA: control, i.e; the yields of the produeto are proportional to the rates at which they are formed. On tho other band, if the producta of a reaction come to equilibrium un.der. the reacti.on conditions the product distribution is said to be thermodynamicallY controlled.

~=CH-CH=CtI:! + HCl

I,i--additlcm, futerl ll, .. addition

CH3-CH-CH=CH2 CH3-CH=CH--CH2-Cl

I CI

n""" stable product) (more .table product)

Sulfonation of naphthalene is another familia~ enmplc.

Pl"Ohleno. 5.14:.

Select the eerreee answer.

(0) The ehange in hybridization stale of the asterisked carbon in the following reaction'

o

II CH,CNH. is

B. sp3_Sp

C. sp-sp2

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62

OlgW'1iC ChemistJy-ProbIem. and Solutions

(b) The m.olecule which behaves both as electrophUe and nucleophile is

. A. CH~NH2 B. CHaC] C. CHaCN D. CHaOH

(e) Which type of reaction occurs when a reactant has a double bond?

A. Addition

B. Elimination C. Hydrolysis

D. None

(d) The m.ost stable earbanien 8J!1(Ing the following is :

CH1- CR - CH - CR -

~6 "9 c9 "9

OCH~ NO, CH.

(e) Which of the foUowi_ng i80)0st effective group il) stobilizing inductively a free

radical? -

A.F

B.I

C. B.r

D. Cl

If) Which of the following is an addition reaction ?

OH

A. CHaCHCH!) ,ili"hol ~--CH=CII:! -+ H· -+ Br-

I

Br

B. CHaCHa -+ C~ ~ CHaCHaCl -+ HCI

C. CHa--CH-CH:i -+ HBr _ CHaCH CHa

I

Br

D. CH:.~Br -+ CN - _ CHaCII:!CN -+ Br r (g) Which of the following carbocati.on ;s most stobie?

A 9- " 9- c 0' " 9-

NO. CI OCH.

(h) Write the true order of C-B. bond weakneaa of tho following alkanes ,

flaCH, R:!CII:!, RCBa, HCHa

I D. m IV

A. I > II > III > IV B. n > m > IV > I

C.m>IV>I>m

D. IV> In> n > I

SolutiOn! (0) C (b) C (e) A (d) C, - N02 electron-withdrawing group Ie) B, because I is the le as t electron-withdrawing inductively if) C (g) D, -OCR:! electron-donating group, stabilizes the cation. (hl A, The .tability of the incipient aIlQ-l radic:a1 is reflected in the C-H bond dissociation energies. The larger the alIQ-J gruups attached, the greater is the .stability of free radicals.

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I CHAPTER I

6

Purification and Structure Determination of Organic Compounds

Problem. 6.1:

Which melle would you expect to absorb at a higher wavelength ?

~ or~

Solution: The diene~ would absorb at II higher wavelength or lower energy because it iii conjugated.

Problem 6.2:

Match the following u.v. absorption maxima (1..""..) with the conwponmng compounds: (a) 235 run (b) 303 run (c) 232 run (d) .2:73 run (e) 232-nm

Solution:

2· co· (jl. ctSb· JY (jl

ctSb

215 +2" 10=235 run

253+30+3,,5=298nm

63

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64

Organic Chemlslrr--f'robIems and Solu!ion.

217 +3 x 5=232nm

253+4x5=273nm

217+3x5=232nm

Problem 6.8,

Which of the following bonds 'Would you expect to be i.r, active 7

(a) Cl-Cl (h) l-Cl (c) H-C-C-H (e-c triple bond)

Solution:

Those bonds which have appreciable dipole moment will be I.r. active,

(a) CI-Cl, No (b) I-Cl, Yes (c) -c ... e-, No (d) 4=r-' No

(e)C-O, Yea

Problem 6.4:

How many different types of protons are present in

(a.) l,2-Dibrom<>-2·methylpropane (b) 1,1,2-Trichloroethane

Would you also observe .epli tting ?

b ?H, Va

Solution: (a) CHJ-?~T;"__H

B.r Br

Two ~ypes of pro tone are present at Cd and CD' and Co' No "plitting between .eHa and - C~ groups is observed as they are nat on adjacentearbon.: They would give rise to different 11. m. r. signals.

CJ Cl Ib 10

(h) Cl-C-C-H

I I

H Ii

Two type" 0 f protons are present and there would be spJitti_ng.

Problem 6.S:

Describe the principle involved in the <:$timation of nitrogen by Kjeldahl's method, Solution: The method is based on the principle that when an organic eompound containing nitrogen is heated with cone. H#O 4.' nitrogen evolved is converted to ommonium sulfate. The

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Purification and Struclure Determination of Organic Compounds

65

ammonium sulfate is treated with sodium hydroxide solution and the mixture is steam. distilled. The llhel'llted NHa gaa ill absorbed in excess standard HpO~_ The amount of NBs evolved and hence the nitrogen is determined by tbe amount of acid neutralized by back titration with standard NaOR solution.

Problem 6,6:

(CI) E:rp lain the various techniques used fOT tbe purification of a liquid. (b) 'If a liq uid distils at a constant tempemture, can an inference be drawn that it i8 pure?

Solution, (0) OietiUation and chmmatography. (b) No,.;t could be an asectrople mixture. Problem 6.7:

Chromategraphie method. have been considered as. the most viable techniques for the separation and purification af compounds. List the different ehromatographie techniques.

Solution: Column chromatograpby, thin layer chromatography (TLC), paper el}romatography, gas liquid chromatography (GLC), high performance liquid chromatography (HPLC) and exclusion chromatography.

Problem 6.8:

Predict tho elution sequence of a mixture of compounds containing chlorcbenzene, p-ore"ol and anthracene, developed on an alumina column uolog a solvent oyotem of progressively Increasing polarity,

Solution: Anthracene ___...... ehlorobeneene _ p·oresol

Since the solvent 8yatem initially employed is non- polar and non-polar compounds are adsorbed usually on alumina, we expect the least polar compound to be eluted first, i.e., anthraeene, p-Cre.sol can fOfm H-bond with the hydroxyl groups on alumina surface (Ai20a.tH..0) eo it isatrougly a.dBOrbed and will be eluted lasL

problem 6.9:

An organic compound on qualitative analysis was round to contain C, Hand N. One gram oOt on Olcidation with CuO and oxygen gave 1.239 g of CO2 and 0.12&.:1 g of H20. A 2 g sample of the compound was digested with cone. Ha.804 and the residue wag dietilled after the addition of <m:eSI! sodium hyilromde sol uticn, The ammonla eval ved was absorbed in 50 mJ of 1 N sulfuric acid, The resulting solution was diluted to 500 ml in a measuring flask, 25 mI of this solution required 21,8 mI oro.05 NaOR for complete neutralintion. Calculate the empirical formula of the compound.

Solution: % C = 1239>< 12 >< 100 = 33.79

44>< 1

% H = 0.1269>< 2>< 100 = 1.41 18>< 1

% N= 25 mI of excess dil Jt..S04 = 21,8 ml of 0.05 N NaOH

. .' 2L8><500

50(1 ml of excess diI H28O, = - - 25 - --

.. 436 ml oCO.OS N NaOH Volume of excess IN H;3O.j = 436 ml of 0.05 N - NaOH

= 436>< 0.05 = 21.8 ml

1

Volume of IN H28O, consumed by NHa = 50 - 21.8 = 28.2 ml

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66

Organic Chemistry-Problems and SokltJons

Now, 28.2 ml of IN H~4 ., 28.2 mI of IN ~

" .28.2 mI of IN - combined nitrogen 28.2 x Ix 14

1000 = 0.3948 g

%N z O~8 x 100 "19.74 % 0 (By difference) • 45.06 Empirical formula :

Ek_nt Pt,.".~ Nomic r»<i&hl iI</D/i"" numbtr Simp~.t rotia
rompotli.Uo~ ",atom.
C 39.79 12 2.82 2
a 1.41 tAl
N 19.74 14 1.41
0 45.06 16 2.82 2 Empirical formula of the compound. is CJlN02 Problem IUn:

A 0.2 g sample of an organic monobasic acid gave on combustion 0.605 g of CO2 and 0.0892 gof~O; 0.183 gofthe acid required 15 wi of 0.1 NNaOH for completeneutralUation. Calculate th.e molecular weight and th.e molecular formula ofthe acid.

Solution: % C " 0.502 x 12 x 100 _ 68 45

44 0.2 .

% H .. 0.0892 x 2x 1)( 100 _ oj, 9

18 0.2 .

% 0 (by difference) = 26.65

Empirical Formula :

Element Puc.f!la#. Atomic iI</otiu. numbeJ- Simplut rotio
oompmlUGn ,. .. igM offJt""",
C 68.45 12 5:7 7
H 4.9 1 4.9 6
0 26.65 16 1.66 2 The empirical furmula ill CADi Empirical Cprmula weight ill 122

Molecular weight of the acid _ 183 .. 122 15><0.1

Since empirical formula weight and molecular formula weight are equal, the molecular fOl"llluia of the acid is also C1HI>2 .

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PurHicaUon and Structure Ostsrmlnallon of Organic Compounds

67

Problem lUI:

A compound on analysis gave C - 54.55%; H:a 9.09% and 0 = 36.26%. Ita vapor density is 44. Find the molecul ar formula of the compound.

Solution: Empirical Formula:
elemi!nt ['erct!nl4Be Mamie j Rolative lIum 00, Simple.t ra.till
compolit-wn ","ishl of alUms
C 54.55 12 I 4 .. 64 2
H 9.09 9.09 4
0 36.26 .16 2.26 Empirical formula i. C2".O

Molecular formula will be (C:zH 0) . where n _ Molecular formula weight

. 4 ~ Empirical formula weight

_ 2xV .• D. _ 2x44_2

« «

So moleeular formula is (C:zH40)2 or C.HS02.

Problem 6.12:

A monobasic acid gave the following data on combustion; 0.419 g of the acid gave 1.058 g of CO2 and 0.186 g of~O, and 0.470 g of the silver salt of the acid produced on ignition 0.222 g of ail ver .. Caleulate the molecular formula of the acid.

SolutIon: % C _ 1.058 x _E._ x 100 _ 58 86

44 0.419 .

% H = 0.1~ x 2 x 1 x 100 _ 4 9

18 OA19 .

% 0 (by dilfersnce) - 28.24

Empirical Formula:

C H o

68.86 4.9 26.24

Aiontie .l1<lali." lIumoor Simplmmtio
woighl of_m.
12 5.74 7
4.9 6
16 1.64 2 hrct!n/.og< oompoaition

Empirical formula i. C.I\.02 Empirical formulr. weight = 122

M lecul . h fth ld (0.470 x 108 107) xl

o - arweJg to - eaC1 = 0.22

= 121.64

Since empirical and molecular formula weigh.",. are the same, 80 molecular formula of the acid i. also C~602 .

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68

Organic Chemloby-Prcblems and Solutions

Problem 6.18:

Elemental analyais of an organic compound gave C ~ 39.98%, H - 6.72% and 0",53.3%; and 0.151 g of the compound on "aporization di8jllaced33.8 ml of air measured at 25' ever wate.r and at a pressure of 746 mm of Hg, Determine its empirical and molecular formula, given that the vapor pressure of water at 25' is 24 mm Hg.

Solutiou: Empirical Formula:

ElemBIl Per«nlc8< Atomic &112';"" numbtr Bimplal rtUio
com~r;lion weight a/atoms
C 39.98 12 3.33
H 6.72 6.72 2
0 &3.3 16 3.33 Empirical formula is CH20 Empirical fO!'UIulawelght g 30

M I ul· .' h WRT 0.161x 0.082" 298 x 1000

.. oec .aTWelg_t", Pv'" 1.

760 (745 - 24) x 33.6

.. U6.6

116.6

Molecular fonnul.n ~ (CRP). where n ~ 3Q ,,3.sa .. 4

= (CH20),

" C.HsO.

Problem 6.14:

A monoaetd base contain" C " 53.3%, H = 15.5% and N = 81.2%. One gram of the chloroplatinate salt of the base gave 0.32 g of platinum on ignition. Calcutate ita molecular formula.

Solution' Empirical Formula,

Atomic &lal;"" "~m"",.

weight '" atoms

---I-----------~----------_i

12 4.44

2 6.95

EI."",nl I Pe""~taK<
oompo&itiDn
_.
C , &!I.3
H I 15.5
N 31.2 S;mpleot ",rio

15.5 2.23

Empirical formula is C2H7N Empiri.cal formula weight", 45

1(195)< 1 )

Molecular weight of the mono acid base = '2 0.39 - 410

=46

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Puri!lcation and Structure Determination of Organic Compounds

69

Since empirical and molecular weights arc same it follows that molecular formula is al!IC C2HrN,

Problem 8.15:

Compound A, C7H u;N, is insol uble in water but dissol yea in d it hydrochlorteecid. A, undergoes no reaction with. nitrous acid, When A is treated with methyl iodide and then with silver oxide B, is fanned, On heating, B forms C, C.H17N, C, adds h,ydrogen in the presence of a catalyst forming D, CJllaN, D, on treatment with methyl iodide and then with silver oxide yields (CHa)aN and E, E can be hydrogenated to 2-methylpentane. Assign structures to compounds A to K

Solution: Since A dissolves in dil HCl, it must. be on amine. A, does not undergo reaction with HN02, 1.1;S no~ primary or secondary amine. Wh.en.A, is heated. with CHaI and Ag20, it forms quaternary ammonium. hydroxide B. On heating B undergoes Hofmann degradation to form an alkene C. Since .nitroge.n appears in C, it fullows that .nitrogen atom is a. part of the ring. C, on hydrogenation, becomes a saturated hydrocarbon. Further exhaustive degradation yield.

(~)3N and E. E ;8 t:\ydrogenated to }ield 4-methylpentane.

CjH'

I

CH.

(A)

(i)CH,.! (i.) AgOH

H~

- bN(C~J;()H(E)

Problem 6.10:

Compound A, CI(,lI::n02' is not soluble in water or in sodium biearbonate, It. gives no uaction with C6HJfflNH2' Refiuxing A, with sod. hydnnide selution, el!tn.ction ofth.e mixture with ether and evaporation of the soh'mt yields S, C~HI.20. Acidification of the NoOH solution (0=80 new compound C, CSH'002 which is optically active. B gives a po~;tive iodoform test. Sugge1!t structure. for A, S and C.

Solution: A is not an arid !IJ; it ill insoluble in water and sodium bicarbonate. It is also not an aldehyde or ketone as;t does not react with C6H5NHNH2. A must be An ester as it is hydrolyzed

by NaOH and the resulting alcohol (S) tssoluble in ether and th .. acid (C) is soluble in NaOH.

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70

OrgerMc Chemlstry---Problams and SolutIons

NaOH

~

CH,CH.CHCH.OH I

CHa

(0)

Soluble In ether

CH,CH.CHCOOH I

CH.

(C) (Optlc.llyactlve)

Problem 6.1.7:

Two compounds A. and B, each containing C = 63.58%, H = 5.96% and N = 9.26% give benzoic acid on oxidation. Both dissolve in NaOH solution with. a red coloration. On reduction A and B yield amioes C and D re"pectlvelY. C, but oot D, can be resolved into optical isomers. What are A and B ?

Solution:

Empirical Formula of A and B

EI~"U!.Rt p.""'''1aRe
""mp<>oili<>11
C 63.58
H 5.96
N 9.26
0 21.2 Atomic &wl"'" number 8impiut .l"OtW
woit/hl of a'""",
12 5.29 8
5.96 II
14 0.66
16 1.32 2 Empirical (onnul" of A and B is C8~02

On reduction both A and B yield amines, therefore, they are isomeric nitroalkanes. The sequence· of reactio!13 can be represented as r"llows :

! Reduction

CeHsCHNH.

I CH)

(c)

(Optloali,)' aCllve)

C..H.CH,CH"NO. (0)

! Reduction C6H.CH.CH.NH.

(0)

(Optically Inactive)

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Purllk:aUon and Struc1ure Determination of Organic Compounds

71

Problem 6.18:

An organic. compound A, contailUl C = 76.6%, H = 6.38% and gives 8 mixture of two isomers B and C whe .. an alkaline solutton of A wae refluxed willt chloroform at 60·. B, being sream volatile W!l8 separated by steam distillation which on oxidation gives an acid D, containing C - 60.67%, H - 4.34%. The acid 0, was also obtained. by heating sodium, Bait of A. at 125·14(1" under PI'f!lUlU1'B. As.ign structural fonnulae to the lettered compounds.

SolutiOD: Empirieal FOI'lll.u1a of A :

£lem.,,' "",""""lag' Atom~ RrlatilM number Sim.plesl ratio
composiJkui. weigh! oralo","
C 76.6 12 6.38 6
H 6.38 6.38 6
0 17.02 16 1.06 :1
Empirical formula of A ill C6H60
Empirical fonnula of D :
EI.nu:rn Percen/IJge ;\Jomic R.IoI~ number Simpk.! ratio
oompmilwn ""'ighl o{alams
C 60.67 12 5.05 7
H 4.34 t 4.34 6
0 34.99 16 2.18 3 Empirical fonnulaof D is C7HS 03 .

A is phenol which undergoes Reimer·Tiemann reaction when treated with chlorotorm and base, It forms o-hydroxy and p-bydroxybenzaldehydea. Since ortho-i!lomer CIOn beateam distilled (due to intramolecular H-bonding),B is the orth» isomer and C the is pam-isomer. B is oxidized to ortho·hydroxybenzoie acid (0) which is also obtained from A by Kolbe reaction. Reactions taking place ean be represented as follows:

2) ~:~: . &CHO.

(B)

(A)

!~U".d

. ,

!OXidation

F"'Y0H ~COOH

OH ~COOH

(D)

¢

CHO (C)

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7.2

Problelll 8.19:

A <:om)l(lund offonnula. C4HI~0, reacts npidly with metallic lIOClium hut not with Lucas reagent.. Treatment of A, with hot CODC. sulfuric acid yields a new cempcund B, C.Hs. If B, is hydrated in aqueous sulfuric acid, a new CODl)l(luod C, C,HIOO is formed. Com)l(lund C, is almoet inert to metallic sodium hut reacts rapidly with Lucas reagent. Assign atructlu"elJ to A, B, and C.

Solutio.D: As A reacts with. m.etallic sodium it is an alcohol. Since it does not react with Lucaa reagent it is 1· alcohol. With cone, ~4 dahydration of A takea place and an alkene B is fonned. Hydration of B again leads to an al.cohol C. Since C reacts rapidly with Lucas reagent, it is a tertiary alcohol.

Sequence of reactions is depleted below :

CH,CHCH.OH

I •

CH,

(A)

a+

CH3~=CH2 CR. (B)

OR

I CH,-C-CR, . I

CR.

(e)

Problelll 8.20:

An organic compound A, CaRloO, does not react with sodium. On treatment with HI, it yields two COIII)I(IuodsB and C. B reacts with sodiUl!! to liberate hydrogen and aIao forms a aalt with. sodium hydro.xids. B can aIao be brominated and the !lUlior prodnct contains two bromine atoms. The eompound C, contains iodine. On treatment with magnesium ill ether, followed by CO2, it lonna acetic acid. What are A, B and C ?

Sollition: A isll.ot alcohol Wi it does not react with Na. A may be an ether. On treatment with HI, A COnn;! aleohol and a halide. As B reacts with Na to liberate hydrogen, B ill alcohol (phenol) and thus C is halide. C reacts with Mg to fonn Grignanl reagent· which reacts with COz to Conn aCOltie acid.

Sequence of reactions can be represented as follows:

CR,

~OCH, III

U -CHal (A)

LOH U

(8)

+ CH,I

(c)

(0) Mg. ethe, (iI)CO,

(i;.) H+1H20

eH,COaH

ProbleJn 6.21:

An alkene A, on ozonolysis yields acetone and an aldehyde. The aldehyde is easily olCidized to an acid B. When B i8 treated with. bromine in the presence of phosphorus, it yeilds a eom)l(lund Cwhieh on. hydrolysis gi.Y1!8 a hydroxy acid D.'!'hiJI acid can aIao be obtained from acetonehy reacti"g it with hy<lrog e n cyan;de followed by hydrolysis. Identify the compounds A, B, e and D.

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PuttJlcaflon 1100 Structure Determl'nation oj Organic Compounds

73

Solution: When acetone is treated with BeN followed by hydrolysis, Dis fnnn.ed. by the following reactions :

CHI 'C=O CB/

.,

HCN

CB., /OH C

CH{ 'COOH

(D)

D can. a1~ be fonned from B by the following sequence of reaeeions :

CH.· H Br,JP CH. BI OH

'c/ ---- 'C/ ---- (D)

CH;· 'COOH CHi 'COOH

(B) (c)

B i& the oxide tion product of th.e fo!lowing aldehyde CH.

)CH-CHO CH.

-

Since the alkene on nsono lysisgives this aldehyde and an aeetone, the alkene i ..

CH"CH..-CH=CCH _(_il_O_, __

CHS' I,' (ii) ZnlH,O CR,

(A)

CH. CH

'CH..-CHO + O=C/ J

CH;·· 'CH,

Problem 8.22:

An organic compound eontains C '" 81.55%,. H " 4.88% and N " 18.6% and bas II vapor density of 51.1;. It evolves ammonia when heated with KOH and reduction with sodium and alcohol fanne II base which reacts with nitrous acid giving "ff nitro~D gllll yielding an alcohol. Thi.B alcohol Can be IOOdi...,d to bemoic acid. What i.s the original substance? Explllin. the II hove ehangee,

SolutIo.n: Empirical Form ula :
Blem~n.t I F'erwnu:we A,.,m;c &l<>li .. nwnher , S;mpk.1 "'Ii"
composW.olI Il);!ight %toP'Us
C I ~ 81.56 12 6 .. 79 7
H 485 4.85 5
N 136 14 0.97 Empirical formula is C,H6N

Mol&cular Cannula weight Molecular formula" (C,H6N). where n "Empirical formula weight

2)(51.5

" . 103 ~ 1

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14

Organic Chamistry-Problems and SalutlOn.

So, molecular formula iB (CrH~N)1 or G1H5N

A 10 amine reacts with lINOa to give Nil. and alcohol. l' amine is fonned by reduction of a nitriles by sodium and alroho!' Nitriles also evolve NH3 when heated with KOH,

Na, C,H,OH H.No,

G6H~GH~NH~ -

C6H~CN 1 KOH

The evidence suggests that the originalsubstanCG is benzonitrile., Problem 6.23:

An arnmntin monobasic acid A. contain C" 70.6% and H., 5.71%. Its metlzyl ester baa a V.D. of75. When A ill distilled with soda lime it giVeB a IIydroc:arbon. On oridation with KMn04 it gives a diabal!ie acid B. Name the compound and three onts isomers. How will you distinguish between these isomers ?

SOlution: Etnpiriolll Formula :

Ek"",nJ P.""ni<Jg< Atomic &ltJti{.~ ,number Simpk.t ratio
comJ1O'rtion ""'iSht ofatmn.
C 70.6 12 5.88 4.0
II 5.71 5.71 3.86
0 23.7 16 1.48 I The Empiriclll formula of the monoaeid ;s G4H.N

Molecular weight oCthe methyl eater = 2 x V.D. ,,2 x 75 .. 150

Molecular weight of acid = 150 - (12, + 2) = 136 (.CH3 of the methyl ester ill replaced by H)

Empiriolll formula weight of the acid = 68

Molecular formula of the acid" (C4H40)n where n " : = 2 = (C.H.O)2 " CJiS02

The acid on dietillatio.o with soda lime gives toluene.

Since A on oxidation with KMn04 givt'J! a dibasie acid, A rould be any one of following isomers.

CH. ~COOH

U

or

9

COOH

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Purlficllllon and Structure Detarmlnation of Organic C(lmpounds

75

B could be any of the following isomers :

COOH COOH ~COOH

. r I

e-, COOH

or

¢OH

COOH

Problem 6.24:

A compound R, with molecular formula, CJII~O is iruroIuble in dil. acid and base. It does not reduce Tollens' reagent but forms a 2,4-dinitrophenylbydrazone .. On vil!(lrotLS o:ridBtion on acidic product CJl604 is formed which forms on acid anhydride on heating. Treatment of R, with sodium hypobromite gives a different acid which, when heated with soda-lime, yields toluene, Propose a structural formula for R.

Soluticm: R is not an aldehyde as it doe. not reduce Tollens' reagent. It must be a ketone as it forms 2,4-dinitrophenylhydrazone" Since the acid anhydride is formed so the two carboxyl groups on benzene ring ore in the ortho poaitions.

The sequence of reaetions ls as follows:

((CH3 COCH, (R)

~ NaOSr ~CH~ ~COOH

exi

(lfCOOH ~ ~COOH-H,O

~n ~

o

vigorous

Problem 6..25:

An organic compound A, contains C .. 90.56% and H .. 9.43%. Ita vapo~ density is 53. On o:ridation A, yeUds a dlbaaie acid B, containing 67.8% C and 3.6% H. The IIilve~!!Ilit of the acid contains 56.8% or.ilver. The acid on heating forms a compound C, of molecular fonnulll CsH40~. On di!ltil1ation with soda-lime, the acid B, forms benzene. Explain the above reactions and assign structural formulae 10 A, B and C.

Solution: Empirical Fonn ula :

Element P.ro/!~ Al<lmlc ReIatI"" number Slmplnt ratio
""",,,.,.illon _jghl o{alom~
C 90.66 12 4
H 9.43 I.U 5 U rheberrcc htl lch gesc h utztes M ateri"

76

. () 53><2

Molecular formula of A • C"H6" where " • ~ ,. 2

= (C" H,,)2 = CSHIO

E.rnpirical Fonnula or the dibaste add (B) :

Eknuml P,rrenmg. Atomic !Mati"" number Simpkst rolio
rornptJ3"~titJr.i to.ighl o{lIlo"",
C 57.8 12 .(.82 4
H 3.8 3.6 3
0 38.6 16 2.41 2 Empirical formula of B is C 4~Oi

_ . (100." lOS )

Mol.ecullU' weight of B = - 56.8 - 107 ,,2 = 166.3

Molecular formula ofB = (C.H302)2'= CAO,

The sequence of reactions .i.e as follows:

(A)

(B)

~ Soda lime. 11.

c

0:>0

° (C)

acCH• I

CH a

0";

-

Problem 8.28:

An orgnnie compound A, con.18ins ('. g 68.85%, H .. 4.9% Il!ld reacts with ~OH; on treatment with NoOH, it· f!ll'rnl! two eompounds B and C. Compound B, ill soluble in HCI and can be oxidized to compound C, with alkaline KMnO,. The compound C, on treatment with cone. HCI forms an acid D, ",hich on he"ting with lID alkali gives phenol, Identify the compounds A. B, C and D. Explain the reactions.

Solution: Empirical Formula of A :

Ehme.nl P ..... nl<t8. Atomic I Relatl"" num~r· SimphU. nlIio
rompwition ,oeigill of~
C 68.85 12 I 5.74 7
H 4.9 1 4.9 6
0 26.25 16 1.64 2 U rheberrec htl lch ge5c h (jutes M ateri"

p u ,mcal i 0. nand S lructu re Oeterml n auon 01 0'9 an lc Compounds

77

Empirical formula of A is C1He0~

Since A reaots with NH20H hence it contains ao aldehyde group. The sequence ef'reacnens can be rep resented as follows- .

NaOH

Cannizzaro reaction

(B)

~ osi

An acid

alkali,l> -CO,

rPyCOOHOA.}

(c)

~ HCI

MCOOH

.

:::-..

HO

(D)

Problem 6..27,

An organic halogen compound A, contain. C '" 66.41%, H '" 5.53% and CI ~ 28.04%, On tre atm en t with potas si urn hydroxide ""I ution gave a hydroxy com pound B, containing C '" 77.77%, H " 7.40% but no halogen. B, on oxidation yielde a monobasic acid C, which on . distill a tion wi th soda Lime gave benzene. Assign structures to A. Band C and describe a method for the preparation 0 r compound A

Soln tion' Empirical Farm ulo of A ,

:1 EI~me.'I1l P,,"",,n/.a8.
compD$il_ion
C 66.41
H 6.53
CI ZS.04 Momic &lntw. number Sim.pIJ.:st rut;"
UH!ight a{alom.o
12 5,53
5,53 7
~M 1),789 Em p irieal r arm ula n r A is C.H,CI Em pirical FOrni ula of B :

EI.mon, p.n:onf.a8. Atomic &/alille >uJmbr,r Simplut mho
composition weichl ofaIamB
C 77.77 12 6.48 69
If 7.41) 7.40 7,9
° 14.83 16 0.93 Em pineal form ula of B is C7HeCI

U rheberrec hil ic~ qesc h ,Jt,tps M ~'~ri "'

78

OJVSl1iC Chemistry-Prcblems and Solution"

Reactions involved arc represented below :

KOH o~

CoH;CHICI ~ C.H,CH20H - CeH.COOH

(A) (B) (C)

t Clio hv

((CH

,

I

~ Soda Iime, ~

c

Compound A can be prepared by photo chlorination of toluene.

Problem 6.28,

A 1.06 g sample of an. organic compound gave on combustion 3.08 g of CO, and 0.54. g of H20. This compound on heating with caustic soda yields an alcohol and. the sodium salt of an acid. Dtstlllataon of the sodium salt of the acid with soda lime gives benzene. Determ.ine the fOrmula for the compound, the alcohol and the acid.

3.08 12

Solution, % G ~ . 44 x L06 x 100 ~ 79.2

% H = 0.54. x ...!.. x 100 = 5 66

18 l06 .

% ° (by difference) ~ 15.14

Empirical Formula of the organic compound :

Element Ptm;ntagl! Atomi. &I<It;"" number Simplnt rat;"
""",pow/o" ,.,.iBM o{o>Iom.
C 79.2 .12 6.6 6.95
H 5.66 5.66 5.96
0 15.14 16 0.95 Empirical formula is GiHeO

2x53 Molecular formula (~HsO)" where n = 106 = 1

Molecular formula is C7"60

The formula or the compound is CsB,CHO The formula of alcohol is CeH:!CH:!0H

The formula of acid is C$H"COOH.

Problem 8.29:

An orga.nic compound A, molecular formula CA02 when treated with ~ ammonia and then heated formed B, molecular Connula C3H,pN. B, when heated with P205 formed C molecular formula CsHsN. 0', on complete hydrolysis formed A. 0', on reduction with a compJe>< metal hydride formed a basic nitrogenoua compound, D, molecular formula CaHgN. D, on

U rhcberrec htl lch gesc h utztes M ateri a

Purification and Stroctu,," Determination 01 O'ganl~ Compounds

79

treatm.ent with nitrous acid fanned an alcohol E, molecular formula CaHaO. E, on oxidation formed compound A. Give the Btruc:tureB of eempounda A, B, C, D and E and e%plain the reactions. Solution: With ammonia A forms amide B. Hence A may be an acid, P205 il! a dehydrating agent, removes H20 from amide Band fer:m!l nitrile. A nitrile on hydrolysis yicldB a ~lic acid.

C31\;°2 NH, C3140N p,o. CaHsN
- -
-11,0
(acid) (runiM) (.utrl1e)
(A.) (B) (el H,O"

Nitrile on reduction yieldB l' amine (O). I' amine can be converted to alcehol (E) by HN02 and the alcohol on oxidation yields on acid.

Reduction ffNO. Oxidation

CsH~N Ca¥ -------- Ca~O CaHa02

-N.

Nitrile

loll- amine

alcohol

acid

(e)

(D)

(El

From above reaericns, it fallows thot

A .. CH.3C~COOH B '" CH,Cu,.CO~

o '" CHsC~CH~2 E = CHsCHzCH~ON

Problem tUG:

A neutral solid A, has the formula CUIH10~. Vigorous oxidation of.A, gives a dibnsie acid B, CaDsOeN. A, can be reduced to B compound C, C',JigN which on oxidation gives a dibwric acid 0, C~04' Compound A, can be obtained by direct nitration of n pnrticul_nr aromatic hydrocarbon. Identify compound. A to D.

Solution: A. is a nitro compound ha vlng two benzene ring fused together. On oxidation the N02 group remains in one benzene ring while the other ring i!< oxidized. Since dibasic acid is formed, A must be nitronaphthalena

&

(A)

Ox;

-

~ .. '.duction

Oxi -

((COOH.·.

I

~

eOOH

U rheberrcc htl lch gesc h (jutes M ateri"

80

Problem 6.31:

A compound A. cont.ain.s C " 48%, H " 4%. Sodium fusion of A reveals the a bsenee of halogen, sulfur and nitrogen. What" is the empirical fonnula of A ? Draw structure of A. Solution: Empirical Formula of A ,

E~mlmt

P.ra:ntag. t:Ol11:poI'itwn

C H o

48 4 48

12 1 18

4 4 S

The empirical fonnulais C.H.Os The compound is succinic anhydride.

~

° (A)

Problem 6.32:

A ketone A. undergoes the haJomnn reaction and on reduction gives a compoundB. On heating with sulfuric acid B, yialds C which fonus a mono o:.onide D, with ozone,. D on hydrolysis in the presence ohinc dust gives ouly acetaldehyde. IdentifY compounds A. B, C and write the chemical reactions involved.

o Solation: Since th,e ketone undergoes the halofonn reaction, it should contain the, -LH3 grouping. The formation of only acetaldehyde on ozonolysis suggeJ!te that the alkene is symmetrical. Th,e sequence of reaction. is the following :

o

II CHsC~CCH~ (A)

CH.CH=CHCH3 . (C)

OH

I CHaCH2CHCHs

(B)

ZnIlI,O

03

_ Ozonide

(0)

2CHsCHO

Problem 6.33:

E1!timate the, \,... of the following compounds ,

,",ctSi>

U rheberrcc htl lch gesc h (jutes Iv! ateri"

Purlflca~on and Struc:tule Determination of Organic Compounds

81

Boluti • ., (.) I ~ ! rh.

co :

253 + 30 + 3 x 6 + 5 ~ 303 DID

217 +4x5 + 5 .. 242 DID

216 + 3 x 10 a 245 DID

(d)U Problem 6.lU:

Interpret-the following n..m. r, spectra of ethyl phenylaeetate.

217 + 2 x 5 = 227 nm

Hz

SIlO

300

200

100

o

0
II
~K3
©
._. ,~ U _l
Solutiom

8.0 7.0 6.0 5.0 •. 0 9.0 2.0 1.0 0 6 (will

o

a II b 0

VC~H"..-cHa

(b) triplet (e) quartet

(a) single; Problem 6.35:

Identify the two geometric isomers ofstilbene, CaH5CH=CHCIlH~. from theirt."... values of 294 DID and 278 nm.

Solutiom Coplanarityts needed for most etTeclive overlap of the II-orbitels and increased. ease of the!!: _. It* tl"ansition. CiII· isomer i8 forced into a nenplanar confonnlltioD due to sterie effects andheru:e it absorbs at higher energy than the tm"",ieo!ner. Coneiderillll these lUIpects, the two iaomC!"!l or stilbene and their \".. values are,

Isomer· fltilbene Ab"orption

Cill • stilbene 278 nm

1hIns . stilbene

294nm

U rheberrcc htl lch gesc h (jutes M ateri"

82

Organic Chemlstl)'-P,obIems IIJ1d SolutIons

Problem 8.36,

What do you understand by chemica! shift?

Soilltion: It is the difference (in ppm) between. resonance frequency of proton being observed and that of tetramethylsilane (TMS).

Ch . en] h·ft Shill downfield frmn TMS (Hz)

em, .. s u . (ppm) - Total spectrometer frequency (MHz)

For example, if 60 MHz spectrometer records a proton that absorbs at 11 frequency 426 Hz downfield from tMS then the chemical shift. is :.

Hz

426 60 MHz ,",7.10 ppm .

. Problem 6.87:

The following dienes have 1..,.,.. at 176 mm, 211 mm and 215 mm respectively. Find out which is which and why?

. CH2=CH, /CH.

(I) H/C=C'H

(iii) CH~=CH-CHr-CH=CH2

SolutioD: Isomer

(0 (ii) (iii)

CH,=CH... /ll

(ii) - 'C=C

H/ 'CH,

Absorption 211nm 216nm 176 run

Coplan a rity is needed fOT thll most effective overlap of the "...,..bitnls and increWled ease of the It -+ Jt* transition. Cis·isome.r (il is fOtted into a non planar conformation. due to sterle effects and hence it absorbs at higher energy than the trans-isomer (ii).

Isomer (iii) doesn't have conjugated double bonds 80 energy difference between HOMO and LUMO is considerable increased compared to other two col\iugated isome r, Th.erefore, it absorb. at the highest energy (lowest wavelength).

Problem 6.88:

How I:>In you differentiate between CH3COOH and CHaCOCHa by i.r. spectrol;C(lPY ?

Solutio!>: We will look for the absorption at about 3201M1600 em-1 wavenumber region in the spectra of both acetic acid and acetone. A broad O--H stretching band is observed in case of acetic acid due to intermolecuJar hydrogen bonding. The broad band is absent in ease of acetone.

Problem 6.39:

What compound (c,~O) has n.m.r. signals at 8 7.3,4.4. and 3.7 ppm with relative intensities of 7 : 2,9 : 1.4 ?

Solutioa: Molecular formula "uggeste the compound contains a benzene ring. Three signals aignlzy that there ore three typea of protons,

The ratio of intensities ~ :

7

5 2

b 2.9

c

1.4

U rheberrcc htl lch gesc h (jutes Iv! ateri"

Purifi<:atlon and Structure Determination of Organic Compounds

83

The SH of 8 (8 7.3) are in the aromatic range, suggesting a monosubstituted benrene.

The IH of c has II "hift expected of alcoholic protons. The 2H of It (8 4.4.) corresponds to ....(:~unit. So the compound is benzyl alcohol;

Problem 6.40:

How many n. m. ".signals would you expect in eaeh of the following ;

(i) CH,-r-1H2 (i.;) CH'4=CH~

Cl Cl Br

Solution: {il l,z.:Dichloropropane (opticnlly active Or inactive) gives four 1>.m.,.. signale.

H'

a b I

CH.-CHCI-C-Cl 10'

H

The environments of the two protons on C-l are notthe same (and no amount of rotation about single bends will make them 80); the protons are not equivalent aud will absorb lit different

field strengths. .

(ii) Z.Bromopropene gives three signals in II.m.r. spectrum,

CH; Hb

'C=C/ Br/· -'W

The environments of the two protons on C-l are not same; these protons are 'nan equivalent and we expect, 11 n. m . r. signal from each proton.

ProbleDl &AI:

Explain the importan ... of finger print region in i .. r. epeetroseopy, How i. the carbonyl frequency in acetone affected when one !If the methyl groups i.n acetone La replaced by (il -Br and (ii) -N~ group. . -

Solutioa: Importance of finger print region (900 - 1400 em-I) ; or (7J.l to llJ.l)

Each organic compound baa its Ol'NIl unique absorption pattern in this region. So by comparing the i. r. spectra or an unknown ecmpound with a standard "pedro recof.ded under identical conditions, the identity of the unknown compound can be guessed, The pattern of i.r. spectrum in the flllger prin tregicn is very sensi ti ve and d lfrera with minor chemical or stereeehenueal alterations in a molecule.

(i) When one of the methyl group. in acetone is replaced by-Br the absorption frequency of the C---O bond is increaaed due to electrenic withdrnwing e.ffect of Br ..

o

II

CH,-C---Br

-

U rheberrec htl lch ge5c h (jutes M ateri"

84

(ji) Whenon__e ofthemetbyl groupII in acetone is replaced Q)' NHz the absorption frequency oCthe C----O bond is decreased due to resonance of the following type as a result of which C-O bond becomes Ie •• than a full double bond.

:0:

II CH(,O'NH.

-

Problem 6.42:

The sharp peak in then.lILr. speetrum ofcyclObeune broadens on rooting and separates into two peaks when the "'m.T. is taken at - too·C. Explain.

Solution: Cyclohexane displays itselfin its spectrum as a .oingIet at room temperature because of rapid inversion (:loa times per second). At - loo'C the molecule is frozen and the energy available for interconversion is reduced, which 0CCIln! fur each conformer to exiBt long enough to he detected by "'lILT. The axial proi<ll:Ul have different chemical shi.ftB compared to the equatorial protons. AI/, a result of this two signals are displayed each corresponding' to the ~al and equatorial hydrogens of the two chair conformations.

~H(e)

Problem 8.43:

Calculate ~. for the fullowing oompounds.The base value given fur enenes is 215 mo. incrementa faT exteooed coqjqgstion 30. U 10; Ii 12; y, " 18 run and homoannular diene component 30.

.~

(IJ)~·

o

(C)~

Solution: (II) Base value " 215 om

E>r:ocylic double bond • 5

2 )( P, 8Ubstituents '- ....

(h) BMIl value ~ 215

Homoennular diene component", 3{1

E>r:ocyUc double bond " 5

y substituent " 18

Ii sub<rtituent " 18

A..u =286nm

(e) Base value - 215 {[ substituent" 10 IJ Bubstituent " 12

."".. = 237 nm

U rheberrcc htl lch gesc h (jutes Iv! ateri"

Purt1icaUon and Structure Determination o! Organlo Compounds

85

Problem6M:

Discuss briefly how the O-H and C--O stretehing frequenciel1 in the Lr. will be shifted

from their routine values in case of methyl salicylate. .

Solation: O-H stretching and C--O atretchin_g frequencies will be lowered in methyl salicylate wheo. compared to their routine values. This la due to intramolecular hydrogen bond present in m.ethylsaJicylate.

~:3

ll;lo,li

The O-H stretching frequencies may be as low as 2800 em-I compared to around 3600 em-I in ordinary hydro:ry compounds.

Problem. 6MI:

.An organic compound A, C4HsO shows sUong absorption at 1070 em-I but noabsorption in the region 1600-1800 em-I in its i.r .. spectrum. Ita .n ..... r. consists of two multipletl! of ratio 1 : 1, centered at 81.8 and li 3.7 respectively. What i8the structure of A?

SOlation:

No abscrption in 1600-1800 em-I range in~r .. sped:rum indicates the ab&enre ofa carbonyl group .. Two multiplets in the ratio on: 1 inn.m.r. indicate symmetricaJnature of the compound. The proposed structure is THF.

aCt

1070 em-I in i.r: corresponds to c-o .stretching. Signal at (j L8 and 83.7 in n.m.r. corresponds to absorption by H4 and Hb respectively.

Problem. 6.47:

CH CHa

3 I

(i) 'C=C-C-H

CH{ II

o

Using Woodward·Fieser rules, calculate ~ values forMt" transitiOIlll ror the foUowing:

CH.

I .

~"C ........ H

(iill.__) ~

(iVlW

SoI1ltion~ (i) Base value a substituent

2 x IJ substituent

......

(ii) Base value

a substituent

2 x b eulmtituent

",210

'" 10 ,,24

=244 urn ",210

" 10 -24

U rheberrcc htl lch gesc h (jutes M ateri"

86

Exocyclie. double bond a fi

.;_· .... 41

1..,,_

(jii) Base value

Three alkyl groups },,_.

(ill) Base value Ceniugated C=C Three alkyl groups Exoeyelic C=G

)",_

Problem 6.47:

How would you distinguish between the following .ketones on the basis of their n.m.r. spectra ?

= 249 run

- 268nm

= 2511 (ciMoid cyclic diene) = lfi

=.253 =30 d5

=5

= 303 run

(A)

,

~H.-tcH,

o (8)

Solution, Although both compounds show the same number of signals (three), they differ in the nmltiplicity of peaks, Signal due to

proton a

b

e

Triplet Quartet Singlet

Multiplioi ty

A B

Singlet Singlet Singlet

In (S) all the signals appear as singlet unlike in fA) where signals of different multipliciti"'! are observed.

Problem 8.48,

How will yell differentiate between salicylio acid and m-hydroxybenzoic acid by i.r. spectroscopy ?

Solution, .Absorption band of )C=O group in salicylic acid appears at a lower frequency than in m-h~!"t>l!ybemoi. acid due to greater predominance or intramolecular hydrogen bond fonnntion in salicylio acid.

Problem 6..49:

An organic eompcund X (mol. formula CsHa0) shows a strong ir. peak at 1690 em-I.

Which of the following structure would you assign to X ?

(0 CsH~CH2CHO (iil C6H~~H=CIl.!. (iii) c"H.c-tJofH. (jv) C8H~COCHs Justif,y your answer.

Solution, X is the keton.e (iv). Ether:e show aboorption band between 1080 - 1300 em -1 and an aldehyde shows around 1.72fi em-I. Only ketones show strong i.r.pcak at 1690 em-I.

U rheberrec htl lch ge5c h utztes M ateri a

P"rilicatioll and SlruCllJr", Oelerrninelian af Organic Compounds

87

Problem &.50:

(a) Indicate tho ,splitting pattern in the n.m.r. spectrum of p·iBopropylacetopheMne. (b) Between acetophenone and cyclohe:r;;yl methyl ketone which will absorb at a lower wave number ?

Solution:

(0) There are five signals inn.m.r. spectrum. Spin-spin splitting ia observed "nly between non-equi valent neighbouring protons i.e .• with different chemiCal shifts.

b

~C/CH~

d0 "y

bC~

CHI CH.

M uJ ti plici ty Doublet Heptet Doublet Doublet Singlet

Signal

"

d

(b)

(I)

an

m absorbs at lower WIIVe number (lower energy as E = hcv). :::C=O group wnjugates with phenyl ring. This effect increases the bond distance of C-O bond and henee low ..... the energy of abeorption . The ."".bony] group in acetyl cyclohe"ene cannot conjuga Ie with cyclohexyi group lind hence absorbs at higher wave number (higher energy).

U rhcbcrrec h II ich gOS" h

ICHAPTERI

7

Alkanes

Problem 7.1:

Draw the etaggered and eclipsed sawhorse drawingl! and Newman projections of 1,1, l·trimethylethane.

Solution:

~H

CHi! CHI

Stanered

H

xfH

CHa CHa

EcliP<led

S.whone drawinp

H~H

CH~CH" H

NeWlnlUl proJection.

ProbleJII 7.2:

Label each carbon atom in the following molecules as primary. secondary and tertiary.

~=d~

~
2
Solution: 2 2 2
3
2
I
88
---- U rheberrcc htl lch gesc h (jutes M ateri"

Alkar.es

Problem 7.3:

(bJ~

Suggest lliPAG name for each of the following alkanes.

(.)~

(e)~

(c)~

")XC( ~)~

Solutiom (II) 4-Ethyl-2,2,3 .6-tetrumethyJheptane (b) 2,2,6,6,7 -Pentamethy loctane (c) 3~Ethy 1- 2-methyloctane (d) 5,6-Di.ethyl-3-methyldecane (t) 5-(2-Methylpropyl) nonane if) 4-Ethyl- 3,3,6-trlmethylheptane (g) 3-Ethyl-.2,5,6-trimethylheplane

Problem 7,4:

Write a complete reaction m.eclumism for the formation of2-brom o- 2_methylpropane by the free radical bromination of 2-methylpropane.

CH,

I Br,

CH.---C--H ----

1 bv

CH~

~H.

CHa-t;'-Br + HBr I

CH3

SoIut:ioJll A free radical mechanism takes place in th ree steps,

hv

Br. __ 2B.'

Propagation step:

CH, 1

CH:r-Q---H + Br' ____

I

CH~

The Br' pulls a H' to generate the most stable radical

CHs I,

CH'4 +Bra----

CH.

Tllrmination Bier." BI"" + BI"" ------ Bra

CH, CH,

1 .. I

CHa--C' + CHa--C'

I I

CH, CH3

CRa I.

CH .--G----Br + Br:

1 CH3

U rheberrec htl lch gcsc h (jutes Iv! ateri a

90

Problem 711,

What is o;:rncking ? How is it 1I1j(!fu1 in the petroleum industry ?

Solution: Crude oil 00 fractional distillation yields 20-25% gasoline. that can be used 118 motor fuel. The yield of hoavier petroleum &actions iaYe!'JI high, Because of the inerensing demMd of high quality petrol, cracking ofhea.vier fuel oils .is undertaken to obtain petro!. Cracking is the pl'OCefl8 of heating of high boiling fracti.OlUI of petroleum at a high temperature to produce lighter fracttona, Cracking involves the d",,"'W' 'of C-C and e--:R bood a, Cracki.ng can be achieved either thermally or using catalysts, The resulting low molecular weight hydrocarbons can be used as raw materials for other industrial proeeeses. Ethylene is 8 petroleum product. It is not obtained from oil wells directly. Ethylene, a rew material of eommerelal importance i. produced by thermal cracking ..

Problem 7,6:

Write structures and names for all the isomeru of the alkane oHonnula CaH".

Solution: leome ra offormula C6R14

(n-B""' ..... ) CRs

I

(4) CHrC~H2CH8

I

CHa (z,2-Dlmethylbut ... ,,)

Problem 7_7:

Write structural formulas for the following compounds:

(0) 3,3-Dimethyl-4-ethylhexane (b) 2,2_Dichlor0-3-brom0-3-methylheptane

(c) nee-Pentane (d) isobutane {e) 2-Cyc!obutyl.3,3-dimethylbeptane if) iso-Octane (g)5-{2;Methylpropyl}-3-metbyldecane (h) 4-lsopropyl-3·metbylbepte.ne

Solution: «(I) ~

(2) CH8C~CFi:JCHCH$ I

CRa (Z-M"tbylpentue)

(3) CR3C~CHCH2CH8 I

CRa (3-MetbyJpe .. ltu!.Q)

(5) CH3CH-CHCHa I I

CRa CHa

(2,3.DlmotbyIbutane)

Cl CJ

(b)~

CH3 'Br

if)~

Problem 7.8:

Which of the iscmeric pentanes can form only one monocbloro aubstitutien product ?

U rhcberrec htl lch gesc h utztes M ateri a

Alkanes

91

Solution! Only neopentane :

Problem 7.9:

What is meant by the term octane number? Also what does it mean by a certain gasoline having all octane rating of 85.

SQlution: Octane number is defined as the percentage by volume ef tao-eetane in B mixt"re of iso-oetaae anda-heptane which. has the same knocking tendency as the fuel under examination.

The octane number is a measure of the quality of a motor fuel, the higher the octane number the better the fuel. Octanenumbers 0.£ 0 and 100 are assigned to heptane and 2,2,4- trimethylpentane respectively. Mature of these two compounds are used to define octane number. An octane number of 85 meanethat the iso-octane and octane mixture COIItains 85% and 15% Ii-.heptane.

Problem 7.10:

m"" reaaons for the followi_ng :

(0) Octane bas a m.p. - 57"C while 2.2,3,3-tetramethylbutone lOl"C. (b) A tertiary free radical is more easily formed than a primary free radical. (c) Ethanol is soluble in water but ethane is not. (d) Methane i8 more stable than other higher alkane a, (~)The quality of a fuel is improved by the addition of tetraethyllead.

Solution: (n) The latter hydrocarbon has a larger surface area. (b) Because a tertiary free radical is more stable. (e) Etban.ol forma H·bond with water. (d) M.ethane is incapable of being fragmented into amaller fragments. (e) It Iunctl.Oll.8 as lin anti-kneek agent and it boosts the octane rating of gasolme,

PrOblem 7.11:

Describe II. mechanism for the formation of benzyl chloride from toluene by photochlorinanon.

~CH~

V (excess) + ci,

,,"u. ~ light

r?YCH,Cl V +HCI

Solution: Initiation step:

CI,

h" -

2ei'

1 (ifl CH.

V +cr-

Propagation step:

CH·

(y·+Cl.-

U rheberrcc htl lch gcsc h (jutes Iv! ateri a

92

Termination step:

lvCU;

cr + cr

+ cl"-

-

Problem 7.12:

Write the major product or each of the following .reactions :

/CH~ Pt RNH,

«(I) CH.CH=C, + H, _ (b) CH3CH~CH#gBr -

- 'CH, '

() hv ,/CH~ ill, P (yCl Na,

(c) CH3 (C + ~ -- (d) CICH2CH'CH~ ___.:___-.. (e) V + CH3CH,I --

VIVOH + CH.CHoMgBr -- (g)CH3~H:! ~ (h) ~CI ~

-t'CI~ (jIO

(j)1-Cl

(j) No reaction (h) >--CH.D

Problem 7.tll

A sample of gaseous hydrocarbon occupying 1.12litre8 at N.T.P. when completely burnt in air produced 2.2 of CO2 and 1.8 If of HzO. Calculate the weisbt of the compound taken and the volume of oxygen at· N.T,P., required for its burning, Find the molecuJar formula of the hydrocarbon.

U rhcberrec htl lch gesc h (jutes M ateri a

93

Solution:

Weight of CO2,, 2.2 g

weight of carbon .. 2.2 x 12 .. 0.8 g

44 .

weight afwater; 1.8 g

weight ofB; ~ xl = 0.2 g

.. .. 0,6 0.2

Atol!Ueratio ,C! H = 12'T = 1:4

Therefore, empirical formula is CH.

Weight of the Izydroearbon , 0.6 + 0.2 = 0.8 g

In 22.41 (1 molar volume) the hydrocarbon is ;:2 ,,22.4 Of 16 g Weight of 1 mole of the Izydrocarbon .. 16 g

Molecular furmula is CH.

. 0.6. 0.2

Moles of oxygen required for C.. 12 and for H .. "2

Total ozygen required - 0.05 + 0.05 .. 0.1 mole.

Problem 7.14.:

A mixture of ethyl· and isopropyl-iodides is heated with metallic sodium in dry ether.

Predict the products.

Solution: Three products are formed according to the Wurtz reaction:

CH3CH2C~CHa' (CBa)2CHCH(CH$)2 and GHa<:H2GB(CHS)2 Problem 7.15:

Indicate with relevant f;<Iuations three different methods for the oonverBion of isobutyl bromide to isobutane.

CHs

Solution: (1) )CHCH.Br

CB.

Mg CBs, :l!oO

ether' _;CBCH,.MgBr-

CH,

CHs CH. HI. Pt

)CHCH3 (3) )CHCHJh'-

CH. CH.

CHa, _;CHCH.

CH.

CHa )CHCH.

C;:H.

CH3

(2) 'CHCH"Br

Car

Problem. 7.16:

Wri.te the possible mono-aubstituticn products that would be obtained by the c:hIorination of isopentane at 300"C. Which isomer would you expeet topredominste ?

Solution: Total number of mono-subBtitutedproducts will be flve. The folowing isomer will pred.ominate being 8. tertiBly alkyl c:hIoride ,

CHI )C-CH.CH.

CHa 61

U rheberrec htl lch gesc h (jutes Iv! ateri a

Problem 7.17:

Write a. balanced equation for the o:ombllBtion of n- butane and show that it is comristent with the general equation- (7.1) [See A Textbook of Organic ChemiBtry by R.K Bansall.

Solution:

1

C4"10 + 62:02 ----- 5"20 + 4CO~

.. -4

(3" + J.) 0 ()- _.- 0 CO

C."2». 2 + --2- ~ ______... .. + 1. ~ + n. ~

PrOblem 7.18:

State the dihe<b"al angle between the bromine atoUll! in each of the foUowing compounds, Br

Br Br

(" H .) "WeH, (dl HWIk

"" C"i7'" "~"

Bt H

Soluticm: An_y conformation of 8 compound can be specified by a dihedral angJe-Ihe angle between the C-H bonds on the front carbon. and C-H bonds on the back carbon atom in. the Newman projection.

(a) SO' (1)) O' (c) 180' (d) SO'

. Ca)

PrOblem 7.19:

Name One isomer of octane which on chlorination will give only one octyJ c:hloride.

CR. CR.

I .21 31 4

CH.-----C----C---- H.

1 1

CH. CH.

Solution:

I. 2, S. S-T.,t ......... thylbutJIDe

Problem 7.20:

OiSCl!.8e the Hammond postulate.

Soluti.oD: The Hammondpostulate provides a convenient and straight forward method for correlation ofreaotivity and ~eetivity. Reactivity implies the tendency of the reagent to rew:t with a substrate while selectivity IDQ8JI,~ preference for ODe out of !leveral reaction pathways. The selectivil),.of free, radiea.l halogenation of alkanea differs con.siderably toward VariOllS halogens. This is demonstrated for the halogenatten of .. -butane,

H H H "

I I I I H-C-C-C-C-H I I I I

H H H H

H 1I H H

x, I I I I

- H---C-C-C-C-H +

I I I I H H H X

56±2% 31± 1% 2±O.5%

H H H H

I I I I lI-C-C-C-C-H

I I I I

H H X H

44±2%

69±1% 98±1%

U rheberrcc htl lch gesc h (jutes M ateri"

95

The relative rat,,~ of formation of the isomerie products i~ primarily controlled by the probability factor and the energy faetcrs. Butane has six prim.l>.ry bydrog<ln and four !!eeOndary hydrogen. atoms. Thus the probability fa.etor results in the formation of primary halide in fluorination in the ratio or 3 : 2. In oth.er words, no selectivity for fluorina.tionla obtained.

In chlorination of n-butane, the sacondary halide i. obtained in 8 yield twice that of the prima.ry product. Chlorination ill still non-selective. Bromtnatton orn.bulane, however, produces the prilllDfY to secondary product in the ratio of 2 : 98. This ahews the energy factor must enhance the rate off ormation of 9econdary product. In short. brominotion is more selective but leas reactive. In other words, bromine shows much greater ability to diserimtnata among the different types of hydrogens.

The selectivity of halogena.tion ill even greater fur abstractam for the tertiary hydrogen atoms WI shown fur .2-methylpropane.

CHs CHa CH3
I X. I I
CH3-C-H -- CH~-C-H + CHs-C-X
I I I
CH3 CH2X CH3
F2 90% 10%
C12 70% 30%
Br:~ 1% 99% In this case there i. no .selectivity for fluorination. But II substantial fraction of chlorination i. tertiary. In contrast, brominntion yeldls the tertiary product almost excl usive1y.

The greater selectivity of bromine can be, explained in terms of the structure of th." transition state, which ia a point of highest energy on the energy on the energy profile diagram.

A useful quantitative guide in thm regard ie the Hammo.nd postulate. It states that in a bighly <WItbennic reaetion the reactants are higher in energy and transiti.on state will be reached eady and resembles the reaetanta (reactant like). In a highly endothermic reaction, the product.'l are high in energy and the tnmsition state will be late and resemble. the products (product like). In short the location of the transition state of the reactant coordinate will VII!)' with tho relative energies of the reagent, transition state and the prodUot.Thi8 ill depieted in the following diagmm.

Transitioo sto.te

Products

P,oducts

Reaction c:oo<dOnate -

U rheberrcc htl lch gesc h (jutes Mate,;"

98

In the highly exothermic reattion, the energy level of the reactanta and the transition sta tea are clOl!e together. The trBnllition ~tate u atso dose to the reactants or it is reached earlier. In the highly endothermic reaction, the transition state is cloee to the prod~ or it u reached late (a high value cf energy of activation).

ProbieUl '1.21,

Explain the struetnrea of the transition 8tates for the chlorination and breminanon of the n-butane on tho basi. of the Hammond postulate.

Sobltion:The foUowing reactions take place for the chlorination. and. bromination ofn-butane :

-

-Hel

- 8 Kcallmole

-HBr

dB + 10 KcaIImoIe

+'1 KcalImole

According to 4H data the f"trst propagation step {ablUacilon of II hydrogen by a halogen atond for chlorination U exothermic while for breminatien it ill endothermic. Therefore, we expect that the transition state for chlorination will resemble the chlorine radical.Thi. is the aame speciel in both reactiolUl (primary 118 well M eecondary hydrogen abetrectiOIUl 80 we would e%peCf. the energies of the transition "tetetl to be vel)' similar. The energy levels of the reaetants and the transition state are dose to each other. The transition 8tate lies closer to the reac:l.ar!ta along the reaction mordinate. This means that in the exothermic step, bond-breaking has not proceeded wry far wben the t;ouWtion state iJj reached «(IT the transition state bB3 achieved very little alkyl radical character).

-

-HCI

* [CHaCH.CH.CH. 111111 H 11"'"l11cll·

CH.CH,CH,CH, + cr

--

-nci

CH,CH.CH.CH.C1 + HCI * [CH.1CH:lYH 111111 H 111"""111 CI]·

CRa

! CI, CHaCH2CHCl + HCI I

CH.

U rhcberrec htl lch gesc h utztes Maler; a

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