Вы находитесь на странице: 1из 15

EXERCISE-II

1.

Explain the following giving proper reasoning: (i) Treatment of 1, 1-dimethyl oxirane with sodium methoxide in methanol gives primarily one product. Also identify the product giving its IUPAC name (ii) Trimethyl amine reacts with alkyl iodide (RI). As the reaction proceeds the reaction rate abnormally increases, inspite of depleting concentration of reactants. (iii) Optically active 2-iodo butane on treatment with NaI*/Acetone gives a product which do not show optical activity. (iv) In the solvent DMSO the order of reactivity of halide ions with methyl bromide is F > Cl > Br > I opposite to that observed in methanol solution. ( n C3 H 7 ) 3 N + CH3 I ( n C3 H7 ) 3 NCH3 + I a.
Relative rates: in hexane, 1; in chloroform, 13000

b.

Br + CH 3OTs CH 3Br + TsO


Relative rate: in methanol, 1, in HMPT, 105

(v) Although ether are weakly polar, are used as solvent of choice for Grignard reagents. (vi) Treatment of either CH 3 CH CH CH 2 Br or CH 3 CH CH CH 2 with
O

Br

2.

3.

aqueous HO gives the same product. Also write down mechanism involved, & IUPAC name of product. On reaction between an alkyl halide and KOH in a mixture of water and ethanol, compare the two mechanism SN1 and SN 2 : a. Relative rate of CH 3 X , C2 H 5 X , iso- C3 H 7 X & tert- C4 H 9 X b. Relative rates for RCl, RBr and RI c. Effect on rate of a rise in temperature d. Effect on rate of increasing water content of the solvent. e. Effect on rate increasing alcohol content of the solvent. In the following reaction is carried out in the weakly ionizing solvent, acetone ( CH 3 ) 2 C = O . (Bs is brosyl, p-bromo benzene sulfonyl)
n C 4 H 9OBs + X n C 4H 9X + BsO
The order of reactivity of halide ions depends or the salt used on their source: if Li + X is used, I > Br > Cl if ( n C4 H 9 ) 4 N X is used Cl > Br > I How do you account for this contrast in behavior?
+

4.

Which of the following is the correct method for synthesizing 4, 4-dimethyl-pent-2-yne, using sodamide in liquid NH 3 ? Given reasons CH 3 CH 3
(i) CH 3C CH + CH 3 C Br (ii) CH 3 C C CH + CH 3I

CH 3 5. Give the product and find all unknowns.

CH 3

(a) H 2 NCH 2CH 2CH 2CH 2Br

CH 3

C2 H 5O A

C2 H 5OH (b) CH C CH Br B 3 2

CH 3
H
(c)

NaI acettone

H
TsCl NaBr A B Pyridine

CH 3 6.

OH

PBr3 C Find out the unknown alphabets.

(a)
O

H 3O CH 3 + CH 3CH 2 MgBr ( 1 eq ) A
+

MgCl
(b) Ph COCl +
H 3O B
+

( 2 eq )
+

H 3O (c) H C OEt + CH 3CH 2 MgBr D

( 2eq )

MgI
(d)

H 3O D

( 1eq.)
CH 2
(e)
HCl E

H 3C 7.

Ph

C2 H 5

To prepare C C2 H 5 by RMgX which is the incorrect pair


OH

2 (a) MgBr + ( C2 H 5 ) 2 CO

H O

(b) C2 H 5 MgBr +

H 5 C2 H 2O (c) C2 H 5 MgBr + COOCH 3


H 2O (d) MgBr + C 2 H 5COOCH 3

H 2O C = O

8. N H 9. 10.

Cl
CHBr3 alc. ( A ) ( B ) KOH t BuO K +

Cl

CH 3 CH CH CH 2 Cl

Zn A Zn Dust

convert?

Zn B Zn Dust CH 3 dry ether What is/are the limitation in the formation of Grignard reagent by RX + Mg

(a) R should not contain any acidic group (b) R should not contain any electronegative group (c) Alkyl halide should not be vicinal dihalide (D) Alkyl halide cant be Tertiary.

11.

Identify the unknowns (a) CH 3 + CH 2Cl + I A

(b) ( CH 3 ) 2 CH Br + KOH ( aq.) B (c) ( CH 3 ) 3 C Br + KCN ( alc .) C (d) ( CH 3 ) 3 C Br + KOH ( aq.) D


Conc.NaOH (e) CH CH CH OH E 1 3 2

dil. NAOH

12.

E2 Write major product of the following reactions: EtOH (i) ClCH 2CH 2CH 2Br + KCN A heat
SF4 (ii) PhCHO B AgF (iii) BrCH 2CH = CHCO 2Me C DMF

13.

(iv) EtOH + HI D (v) EtOH + HCN E

State at least one characteristic test which can distinguish (i) C2 H 5OH from CHCl3 (ii) Halogen atoms present in CHCl 3 and CH 2 = CHCl
(iii) 1, 1-dibromoethane from 1, 2Dibromethane (iv) Chlorobenzene from chlorocyclohexane

(v) oChlorotoluene from benzyl chloride (vi) n-Hexane, CH 3CH = CHCl ,CH 2 = CHCH2 Cl and CH 3CH 2CH 2Cl

14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29.

CH 3 CH 2 I reacts more rapidly with strong base in comparison to CD3CH 2 I 2-chloro-3-methylbutane on treatment with alcoholic potash give 2-methylbutene-2 as major product. Iodoform gives precipitate with AgNO3 on heating while CHCl3 does not. Hydrogen atom of chloroform is definitely acidic, but that of methane is not. A small amount of alcohol is added to chloroform bottles Treatment of Me3CCH = CH 2 and Me 3CCHOHMe with concentrated hydrochloric acid gives the same tow isomeric alkyl chlorides what are these two products. Iodine reacts with alcohols to give alkyl iodine only in presence of phosphorous. KCN reacts with RI to give alkyl cyanide, while AgCN results in isocyanide as major product.
+ The carbocation F3C C < is unstable whereas carbocation F3C is more stable Dry gaseous hydro halogen acid and not their aqueous solutions are used to prepare alkyl halides from alkenes. RCl is hydrolysed to ROH slowly but reaction fasters on addition of KI. + + The mechanism of decomposition of Me3S OH is S N 2 whereas of Me3 S I is S N 1. +

Alkaline hydrolysis of benzyl chloride in 50% aqueous acetone proceeds by both S N 2 and S N 1 mechanism, when water is used as solvent, mechanism was no mainly S N 1. Ethanol is less reactive than methanol as well as isopropyl alcohols when treated with dry HCl gas. Anhydrous AlCl3 is used as catalyst in friedel craft alkylation. Arrange following compounds according to their reactivity with alc silver nitrate t-Butyl chloride, sec butyl chloride and CCl 4 . (a)
H 2SO4 NBS CH 2 OH A B HBr LiAlD4

30.

( i ) Li D ( ii ) CuF

C E G alc.KOH I H
+B NBS h 2 Ni

CH 3

(b) CH 3CH 2CH 2


H
( i ) TsCl
( ii ) C2H 5O K +

OH

( ii )C H O s 2 5T

( i)K

What are (A) and (B) explain giving their stereochemistry

( A)

( B)

31.

n BuLi n C10 H 21Br + HC CNa A B

32.

+ 5-methyl-1-hexene + HBr (peroxides) C B D lindlar's cat H2 E

peroxybenzoic acid

Complete the following by providing (A), (B), (C) and (D): PBr3 NH3 Alc . KOH HBr (i) CH 3CH 2 CH 2 OH ( A ) ( B ) ( C ) ( D )
H+ H O SOCl
NBS Alc .KOH B ) HBr ( (iii) CH 3CH 2CH = CH 2 (A ) ( C Light

Alc. KOH H 2 2 (ii) CH 3CH 2 CH 2 I ( A) ( B) ( C) ( D) LiAlH 4

HBr Alc .KOH 3 2 (iv) CH 3CH 2 MgBr ( A ) ( B ) (C CH CHO H O

33.

Carry out following conversions


Cl

(a)CH CH CH CH CH CH 3 Cl 3 3 2 2

without using peroxide

(b) CH 3 CH 2 CH 2 Cl CH 3 CH CH 3 in single step


Cl

CH 2 Br
(c)

Br

Cl

in three steps only

CH 2 Cl

(d)
O

in three steps only

(e)Ph CH C Cl Ph CH Cl 2 2
O

(f) Ph CH 2 Cl Ph CH 2 C Cl

EXERCISE-III

1.

2.

3.

4.

5.

6.

7.

8.

9.

A primary alkyl halide (X) C4 H 4 Br reacted with alcoholic KOH give (Y). (Y) reacts with HBr to give (Z) an isomer of (X). On reacting with alkali metal such as sodium/dry ether gives (S) C8 H18 which was different from the compound produced when n-butylbromide was treated with Na. What (X), (Y), (Z) and (S) On electrolysis an aqueous ethanolic solution of sodium chloride gives sweet smelling liquid (X). (X) gives isocyanines test and condenses with acetone to from hypnotic (Y). What are (X) and (Y)? The alkyl halide C4 H 9 Br ( A ) reacts with alcoholic KOH and gives an alkene (B), which reacts with bromide to give dibromide (C). (C) is transformed with KOH & sodamide to gas (D) which forms a precipitate when passed through an ammonical silver nitrate solution. Give the structure formulae of the compounds (A), (B), (C) and (D) and explain reactions involved. An unsaturated hydrocarbon (A) C6 H10 readily gives (B) on treatment with NaNH 2 in liquid NH 3 . When (B) is allowed to react with 1-chloropropane, a compound (C) is obtained. On partial hydrogenation in the presence of Lindlar catalyst, (C) gives (D), C9 H18 . On ozonolysis (D) gives 2, 2-dimethylpropanal and 1-butanal. Give structures of (A) to (E) with proper reasoning. One mole of each bromoderivative (A) and NH 3 react to give one mole of an organic compound (B). (B) reacts with CH 3I to give (C). Both (B) and (C) react with HNO2 to give compounds (D) and (E), respectively. (D) on oxidation and subsequent decarboxylation gives 2-methoxy-2-methylpropane. Give structures of (A) to (E) with proper reasoning. A Chloro derivative (A) on treatment with zinc-copper couple gives a hydcarbon with five carbon atoms. When A is dissolved in either and treated with sodium, 2, 2, 5, 5tetramethylhexane is obtained. What is the original compound A? A primary alkyl halide (A) C4 H 9 Br reacted with alcoholic KOH to give (B). (B) reacts with HBr to give (C) an isomers of (A). (A) on reacting with sodium gives (D) C8 H18 which was different from the compound produced when n-butylbromide was treated with Na. What are (A), (B), (C) and (D). One mole of a hydrocarbon (A) reacts with 1 mole of bromine giving a dibromo compound C5 H10 Br2 . (A) on treatment with cold dilute alkaline KMnO4 solution forms a compound C5 H 12O2 . on ozonolysis (A) gives equimolar quantities of propanone and ethanal. Deduce structure of (A) A hydrocarbon (A) was found to contain 85.7% carbon and 14.3%H. This compound consumes 1 molar equivalent of hydrogen to give a saturated hydrocarbon. 1 g of (A) just

10.

11.

12.

13.

decolorized 38.05 of 5% solution by weight of Br2 in CCl4 . Compound (A) on oxidation with conc. KMnO4 gave a compound (C), C4 H 8O and (B) acetic acid. Compound (C) can easily be prepared by the action of acidic aqueous mercuric sulphate on 2-butyne. Deduce (A), (B) and (C). When a hydrocarbon (A) is treated with excess of hydrogen chloride, a dihalogen derivative (B) is obtained. The compound (B) is treated separately with aqueous and alcoholic KOH to give compounds (C) and (A) respectively both having three carbon atoms. Compound (C) does not reduces Tollens reagent and compound (A) give white precipitate with ammonical silver nitrate. Assign structures to compounds (A) to (C). An organic compound (A) C7 H15Cl on treatment with alcoholic caustic potash gives a hydrocarbon (B) C7 H14 . (B) on treatment with ozone and subsequent hydrolysis gives acetone and butyraldehyde. What are (A) and (B). Explain reactions. A dihalogen derivatives (A) of a hydrocarbon having two carbon atoms reacts with alcoholic potash and forms another hydrocarbon which gives a red precipitate with ammonical cuprous chloride. Compound (A) gives an aldehyde when treated with KOH (aq.). What is (A)? A white precipitate was formed slowly when AgNO3 was added to a compound (A) with molecular formula C 6 H13Cl . Compound (A) on treatment with hot alcoholic KOH gave a mixture of two isomeric alkenes (B) and (C) having formula C6 H12 . The mixture of (B) and (C) on ozonolysis furnished four compounds (i) CH 3CHO (ii) C2 H 5CHO (iii) CH 3COCH 3 (iv) ( CH 3 ) 2 CH . CHO 0.369g of a bromo derivative of a hydrocarbon (A) when vaporized occupied 67.2 mL at NTP. (A) on reaction with aqueous NaOH gives (B). (B) when passed over alumina at 250C gives a neutral compound (C) while at 350C it gives a hydrocarbon (D). (D) when heated with HBr gives an isomer of (A). When (D) is treated with dil H 2 SO4 , (E) is obtained. Identify (A) to (E) and explain the reactions. An organic compound (X) on analysis gives 24.24% C, 4.04% H. Further sodium extract of 1.0 g of (X) gives 2.90 g of AgCl with acidified AgNO3 solution. The compound (X) may be represent by two isomeric structure (Y) and (Z). (Y) on treatment with aqueous KOH solution gives a dihydroxy compound, while (Z) on similar treatment gives ethanal. Find out (X), (Y) and (Z). A chloro compound (A) showed the following properties: (i) Decolourized bromine in CCl 4
(ii) Absorbed hydrogen catalytically. (iii) Gave a precipitate with ammonical cuprous chloride (iv) When vaporised 1.49 g of (A) gave 448 mL of vapours at STP. Identify (A) and write down the equations of reaction.

14.

15.

16.

EXERCISE-III

CH 3 O CH 3 CH 3 CH CH2
OH

1.

(i)

attack take place on less sterically carbon

4. 5.

(ii) (a) N H Me
(c) (A)Me C = CH Me,

Me
(B) Me C = CH Me , 2

Me
(C)Me C CH Me 2

OEt

I
(d) (A)

H Me

H OTs

H
(B)

Br
(C)

H Me

H Br
OH

Me

6.

(a)

Et OH

(b) Ph C

OH (c) Et CH Et (d)

CH 2 CH 2 OH

(e)

Cl

Ph

7. 8.

(d)
Br A B

N H

9.

A
Conversion

CH3 CH CH = CH 2 CH 3 ( 1) NaNH 2
CH 3

B C C C = C = Cl
C ( 2 ) H 2 Pd BaSO4

10. 11.

(a) & (c) (a) A Et I (b) B CH 3 CH OH (c ) Me2C = CH 2 (d) Me2C = CH 2

OH O (e) Me CH CH & Me OH CH 2 2 OH 12. The mechanism of (i) ClCH 2CH 2CH 2CN (iii) FCH 2CH = CHCO2 Me
(v) no reaction (ii) PhCHF2 (iv) EtI

13.

(i) Chloroform responds carbylamines test while ethyl alcohol does not. Carbylamine test. The compound is heated with aniline and alcoholic caustic potash-an obnoxious smell of phenyl isocyanide ( C6 H 5 NC ) is produced.
(ii) Chlorine atoms of chloroform can be easily replaced by OH groups on treatment with NaOH. Hence chlorine atoms come in the form of sodium chloride. The solution thus when treated with silver nitrate solution gives white precipitate of silver chloride. Chlorine atom in vinyl NaOH , hence it does not give chloride is not readily replaced by

precipitate with AgNO3 solution. (iii) The two compounds are hydrolysed with aqueous NaOH when 1, 1dibromethane form acetaldehyde while 1, 2-dibromoethane gives glycol. (iv) Chlorine atom in chlorobenzene is very less reactive, while chlorine in cyclohexyl chloride is very reactive. Hence the two can be differentiated as above in (ii) (v) Apply test (ii) as above, when benzyl chloride gives white precipitate with AgNO3 solution, while O chlorotoluene does not give precipitate. Alternately, the compounds are oxidised when o-chlorotoluene give ochlorobenzoic acid when benzyl chloride gives benzoic acid (having no chlorine). (vi) n-Hexane does not respond Cl ion test even after fusion with Na and

AgNO3 . The remaining three compounds are distinguished by their reactivity with alcoholic AgNO3 solution. (a) CH 3 CH = CHCl (a vinylic chloride) does not react with alc. AgNO3 even on heating (b) CH 2 = CHCH 2Cl (an allylic chloride) is the most reactive and precipitate AgCl in the cold.
treatment with acidic

14.

(c) CH 3 CH 2 CH 2 Cl gives precipitate of AgCl on warming with Alc. AgNO3 The elimination of HI (or DI) in presence of strong base shows E2 elimination. The rate determining step involves breaking up of C H (or CD) bond. The CD bond being stronger than CH and thus elimination is faster in case of CH 3 CH 2 I
( ) H 3C CH CH CH3 CH3 C = CH CH + CH CH CH CH 3 3 2
KOH alc

15.

CH 3 Cl

major

CH 3

min or

CH 3

Elimination occurs according to saytzeff rule. The major product is one which involves elimination of H from less hydrogenated carbon.

16. 17.

18. 19.

CI bond being less stable than CCl bond and thus on heating heterolytic cleavage of CI form I which gives yellow precipitate with AgNO3 . Due to three electronegative chlorine atoms present on carbon, the latter acquires a partial positive charge due to I effect of chlorine with the result it tends to attract electrons of the CH bond towards itself. Hence the removal of hydrogen atom as proton becomes easier. Alcohol acts as negative catalyst for oxidation of chloroform. Also it reacts with COCl 2 to give harmless diethyl carbonate. Carbonium ions can undergo rearrangement from less stable to more stable ones. Both compounds give the same carbonium ion initially. Hence Me
( ) +H Me3CCHOHMe Me2 C C +HMe Me3 CCH = CH2 Cl ( ii ) H 2O
i H+
+

rearrangement

Me3CCHClMe 20.

Cl Me2 C CHMe2 Me2 CClCHMe2

Both give the same two isomeric chloride in the same proportions, with the tertiary chloride predominating.

Phosphorus reacts with I 2 to give PI 3 which replaces OH group of alcohol to produce RI 2 P + 3I2 2 PI3

3R OH + PI3 3RI + H3 PO3


21.
+ KCN is an ionic compound K ( : C N :) in which both C and N carry a lone pair electron. Carbon carrying lone pair of electrons is more reactive and thus alkyl attacks carbon to give alkyl cyanide AgCN being covalent has Ag C N : structure with lone pair on N thus R attacks N atom and R N = C is formed.

22.

The strongI.E of fluorine atom in F3C C < produce partial +ve charge on C atom of CF3 which untimately increase +ve charge on 2nd carbon atom to destabilize it F F C
+ In F3C , the F unshared pair of electrons in the p orbitals of each of the fluorine + atom are shifted to C + via pp orbital overlapping and thus stabilizing F3C ion.

23. 24.

Dry gaseous hydro halogen acids are better electrophile. Also in aqueous solution H 2O acting as nucleophile may produce alcohol. KI reacts with RCl to form RI. This RI molecule now hydrolysed easily to give ROH because alkyl iodide are more reactive than alkyl chloride. HOH RCl + KI RI ROH ( more fast ) The more pronounced the nucleophilic activity of the attacking reagent, then the more the S N 2 mechanism will be favoured. Since in S N 1 mechanism the reagent does not enter into the rate determining step of ionisation. However it can also be expected that as the nucleophilic activity is so slow that the mechanism will change from S N 2 to S N 1 . The dielectric constant of water is greater than that of aqueous acetone, and so ionisation of benzyl chloride is facilitated. On moving from 3 to 1 alcohol rate of S N 2 reaction decreases and reaches to minimum and mechanism change from S N 2 to S N 1 . Then rate of S N 1 rate of reaction increases. Anhydrous AlCl3 is used as a catalyst in friedel crafts alkylation. tert-Butyl chloride, sec butyl chloride and CCl 4 with alc. Silver nitrate

25.

26. 27. 28. 29.

Me3C Cl >

CH 3 C2 H 5

CHCl > CCl4

Br 30. (a) A B
C

D Br D

CuLi F

Br

Br

Me (b) (A) OEt H Pr (B) Pr

Me EtO H

31.

A C10H 21 C CH

B C10 H 21 C CL i

C C C C C C Br Cl

D C10 H 21 C C CH 2) 4 (

CH 3 CH

CH3

CH 3 E C10 H 21 C = C ( CH 2 ) 4 CH CH3 H 32. H CH 3 F C10 H 21 C = C ( CH2 ) 4 CH CH3 H O H

C , CH 3CHBrCH 3 D, CH3 CHNH 2 CH 3 (i) A, CH 3CH 2CH 2Br ; B, CH 3CH = CH 2 C , CH 3CHClCH 3 D, CH 3CH 2CH 2 (ii) A, CH 3CH = CH 2 B, CH 3CHOHCH 3 (iii) A, CH 3CHBrCH =CH 2 B, CH 2 = CH CH = CH 2 C , CH 3CHBrCH = CH 2 & CH 3CH = CH CH 2 Br (iv) A, CH 3CH 2CHOHCH 3 B, CH 3CH 2CHBrCH 3 C , CH 3CH = CH CH 3

EXERCISE-III

Br

1.

CH 3 CH CH2 Cl CH 3

CH 3 C = CH2 CH 3

CH 3 C CH3
2 Bromo 2 methyl propane ( Z ) ( isomer of X )

(X)

(Y )

CH 3

( CH 3 ) 2 CH CH 2 CH2 CH ( CH3 ) 2
( 2,5dimethyl Hexane ) ( S)
2. (Y) CH 3 C CH 3 3. CCl3
CH 3CH 2CH = CH 2

OH

Chloretone (Hypnotic)
CH 3CH 2CH 2CH 2 Br

CH 3 CH 2 CH CH 2
Br ( C) Br

( A)
CH 3 CH 2 C CH ( D)

( B)

4.

+ ( CH 3 ) 3 C C CH ( CH3 ) 3 C C C Na ( CH3 ) 3

C C CH2 CH2 CH3

( A)

( B)

( C)

( CH 3 ) 3 C CH = CHCH 2 CH2 CH3 ( D)


OCH 3
5. CH 3 C ( CH3 ) CH2 CH2 Br

OCH 3
CH 3 C ( CH3 ) CH2 CH2 NH2

( A)

( B)

OCH 3
CH 3 C ( CH 3 ) CH2 CH2 NHCH3

OCH 3
CH 3 C ( CH3 ) CH2 CH2 OH

( C)

( D)

OCH 3 CH 3 CH CH 2 CH 2 N N O 6.

E) ( CH 3 ) 3 (C CH 2Cl
CH 3

CH 3

CH 3 CH 3 C = CH

7.

CH 3 CH CH2 Br

( A)
CH 3 H 3C C CH3
Br ( C)

( B)
CH 3 CH 3 CH 3 CH CH 2 CH 2 CH CH3
Br ( D)

8.

CH 3 CH 3

CH 3
C =C

( A)
9.

CH 3CH 2 CH 3

C = CH CH 3

CH 3COOH

CH 3CH 2 CH 3 ( C)
O

C =O

( A)
Cl

( B)

10.

CH 3 C CH

CH 3 C CH 3
Cl ( B)

CH 3 C CH 3

( A)
CH 3 11.
CH 3 ( CH 2 ) 3 C Cl

( C)
CH 3 ( CH 2 ) 2 CH = C ( CH3 ) 3

CH 3

( A)

( B)

12.

H 3C CHX 2 ( X = Halogen )
CH 3 CH 3 C =C

13. ( CH 3 ) 2 CH CHCH2 CH3 ( CH 3 ) 2 CH CH = CHCH3


Br

C2 H 5 H

( A)
14. (A) CH 3CH 2CH 2Br (D) CH 3 CH = CH 2

( B)

( C)

(B) CH 3CH 2CH 2OH (C) CH 3CH 2CH 2OCH 2CH 2CH 3 (E) CH 3CH ( OH ) CH3 (Z) CH 3CH
Cl Cl

15. 16.

(X) C2 H 4Cl2 , (Y) Cl CH 2CH 2 Cl , HC C CH 2 Cl

Вам также может понравиться