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Published on: 08/10/2019
Haloalkanes and Haloarenes
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1.
Carbon compounds containing more than one halogen atom are usually called polyhalogen compounds. Polyhalogen compounds are useful in industry and agriculture. One of the important polyhalogen compound is used as an insecticide.
(i) Name the polyhalogen compound for which Paul Muller won the Nobel Prize in medicine and physiology. Draw its structure also.
(ii) Why is the use of DDT banned in some countries?
(iii) What values do you derive from the answer of above question?
2.
Haloalkanes contain halogen atoms (s) attached to the sp3-hybridised carbon atom of an alkyl group. Many halogen containing organic compounds occur in nature and some of them are clinically useful.
(i) Prove the importance of halogen containing organic compounds with the help of three examples.
(ii) Mention the values associated with your reply.
3.
Some halogen containing compounds are useful in daily life. Some compounds of this class are responsible for exposure of flora and fauna to more and more of UV light which causes destruction to a great extent. Name the class of these halo compounds. In your opinion, what should be done to minimise harmful effects of these compounds.
4.
Benzene on reaction with HOCI in presence of an acid produces organic compound (A), (A) on treatment with NaNH2/liq. NH3 furnishes another organic compound (B). (B) on treatment with HBF4 affords an organic compound (C) wich on heating with NaNO2 gives organic compound (D). Identify (A), (B), (C) and (D).
5.
(R)-2- Bromooctane reacts with NaSH to form (S)-2- octanethiol with inversion of configuration at the stereocentre.How can we obtain (R)-2 octanethiol from (R)-2-bromoctane?
6.
Explain the following in one or two sentences
(i) Displacement of cyanic and amide ion is never observed in nucleophilic substitution reactions.
(ii) RCI is hydrolysed to ROH slowly but the reaction is rapid if a catalytic amount of KI is added to the reaction mixture.
7.
Wurtz reaction falils in case of tert-alkyl halides. Explain.
8.
Explain why chorination of n-butane in presence of light at 298 K gives a mixture of 72% of 2-chlorobutane and 28 % of 1-chlorobutane.
9.
Explain why alkyl halides are generally not prepared in the laboratory by free radical halogenation of alkanes.
1.
(i) The polyhalogen compound for which Paul Muller was awarded the Nobel Prize is DDT. (Dichlorodiphenyltrichloroethane). The structure of DOT is given below:
(ii) The use of DOT is banned in some countries because:
(a) it is toxic to aquatic life.
(b) it is not degraded rapidly by soil microorganisms due to its complex structure.
(c) it is not metabolized rapidly by animals and deposited in the fatty tissues.
(d) Because of its stability, it accumulates in food chain leading to biomagnification.
(iii) Environmental protection and sensitivity towards life.
2.
(i) Halogen containing organic compounds are useful in industry as well as in day to day life.
For example:
(a) Chloramphenicol: It is a chlorine containing antibiotic produced by soil microbes. It is very effective for the treatment of typhoid fever.
(b) Thyroxine: It is an iodine containing hormone secreted by the thyroid gland in our body. This hormone regulates the metabolic rate of the body and maintains basal metabolic rate. Deficiency of this hormone causes goitre. This disease can be prevented by taking iodised salt and sea foods.
(c) Chloroquine: It is a drug used for the treatment of malaria.
(ii) Awareness about the halogen containing organic compounds which are used for the treatment of diseases like typhoid and malaria and importance of iodine in our diet.
3.
CFC (chlorofluoro carbons) are responsible for the destruction of ozone layer and UV light can reach earth which may cause skin cancer and affect flora and fauna.
These compounds should be banned and their use should be made to minimum extent.
4.
(i) HOCI in presence of an acid generates the reactive electrophile, chloronium ion «r, which attacks benzene to give chlorobenzene (A).
(ii) Chlorobenzene (A) on treatment with NaNH2/liq. NH3 undergaes-dehydrohalogenation via benzyne to afford aniline (B).
(iii) Aniline (B) on treatment with HBF4 forms the corresponding salt anilinium tetrafluoroborate (C) which on heating with NaNO2 undergoes Balz-Schiemann reaction through the intermedium formation of benzenediazonium tetrafluoroborate to afford fluorobenzene (D).
5.
We know that SN2 reactions proceed with inversion of configuration at the stereocentre. If, however, two SN2 reactions are carried out at the same stereocentre of a compound, retention of configuration will occur. Thus, (R)-2-octanethiol can be obtained from (R)-2-bromooctane by first reacting it with Nal in acetone and then with NaSH in ethanol
6.
(i) HCN (PKa 10) and NH3 (PKa 11·25) are very weak: acids. Therefore, their conjugate bases, i.e., CN- ion and NH2 - are very strong bases. Since strong bases are bad leaving groups, their displacement in nucleophilic substitution reactions is never observed,
(ii) Iodide ion is a powerful nucleophile and hence reacts rapidly with RCI to form RI,
Further because 1- ion is a better leaving group than Cl- ion, therefore, RI is more rapidly hydrolysed than RCI to form ROH,
The I- ion thus regenerated recycles in the above reaction thereby explaining its catalytic effect.
7.
tert-Alkyl halides prefer to undergo dehydrohalogenation in presence of a strong base such as Na metal instead of undergoing Wurtz reaction as explained below:
\(\underset{tert-Butyl\ bromide}{(CH_3)_3C-Br}+2Na\longrightarrow\underset{tert-Butylsodium}{(CH_3)_3Na^+}+Na^+Br^-\)
Thus, only rand 2° alkyl halides undergo Wurtz reaction while 3° alkyl halides prefer to undergo dehydrohalogenation to form alkenes.
8.
According to the question,
The relative ratios of these two isomeric chlorobutanes can be easily calculated by knowing: (i) the number and type of hydrogens (i.e. 1°, 2° or 3°) to be substituted and (ii) their relative rates of substitution (i.e. I : 3·8 : 5·0 for CI2 at 298 K). Thus
\({1-Chlorobutane\over 2-Chlorobutane}={No.\ of\ 1^0H\over No.\ of\ 2^0H}\times{Reactivity\ o\ 1^0H\over Reaativity\ of\ 2^0H}={6\over 4}\times{1\over 3.8}={6\over 15.2}={28./.\over 72./.}\)
9.
Free radical halogenation is not a suitable method for laboratory synthesis of alkyl halides because of the following two reasons :
(i) It gives a mixture of isomeric monohalogenated products whose boiling points are so close that they cannot be easily separated in the laboratory.
(ii) Polyhalogenation may also occur to some extent thereby making the mixture more complex and hence more difficult to separate.
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