1. The document discusses the classification, nomenclature, preparation, properties and reactions of haloalkanes and haloarenes.
2. It describes the nucleophilic substitution reactions of haloalkanes which can proceed by either SN1 or SN2 mechanisms. SN1 reactions give racemic mixtures while SN2 reactions invert configuration.
3. The stereochemistry of nucleophilic substitution reactions is also discussed including terms like chiral centers, enantiomers and retention or inversion of configuration.
1. The document discusses the classification, nomenclature, preparation, properties and reactions of haloalkanes and haloarenes.
2. It describes the nucleophilic substitution reactions of haloalkanes which can proceed by either SN1 or SN2 mechanisms. SN1 reactions give racemic mixtures while SN2 reactions invert configuration.
3. The stereochemistry of nucleophilic substitution reactions is also discussed including terms like chiral centers, enantiomers and retention or inversion of configuration.
1. The document discusses the classification, nomenclature, preparation, properties and reactions of haloalkanes and haloarenes.
2. It describes the nucleophilic substitution reactions of haloalkanes which can proceed by either SN1 or SN2 mechanisms. SN1 reactions give racemic mixtures while SN2 reactions invert configuration.
3. The stereochemistry of nucleophilic substitution reactions is also discussed including terms like chiral centers, enantiomers and retention or inversion of configuration.
Allylic -> CH 2 =CH-CH 2 X, Benzylic Benzylic chloride 1-phenyl Chloro methane 3. sp 2 Vinylic CH 3 CH=CX , arylic C 6 H 5 X 4. Nomenclature:-
o-, m-, p- dichloro Benzene
5. Preparation of alkyl halide: - (i) from alcohol
(ii) From Hydrocarbon: - Free radicle/ Electrophilic substitution/ sandmeyers reaction/ alkene (a) Free radicle
(b)Electrophilic Substitution
(c)Sandmeyers reaction
(d) Form alkene Markonikovs rule CH 3 CH=CH 2 + HI -----> CH 3 -CHI-CH 3
(iii) Halogen exchange method Finkelstein
Swarts RCl/Br + AgF/H 2 F 2 /CoF 2 /SbF 3 -------> RF + - - - - 6. Properties:- (i) RCl Colourless & RBr/RI coloured when exposed to light (ii) b.p. RI > RBr > RCl > RF (due to molar mass) b.p. decreases on branching m.p increases on branching m.p of p- > ortho due to crystal lattice (iii) Insoluble in water due to no hydrogen bonding. (iv) Nucleophilic substitution reaction: - When strong nucleophile replaces weaker nucleophile is called nucleophilic substitution reaction. RX + NaOH/HOH/NaOR/NaI/NH 3 -------> ROH/ROH/R-O-R/RI/RNH 2
RX + KCN/AgCN/KNO/AgNO 2 /RCOOAg/LiAlH 4 ---------> RCN/RNC/R-ONO/RNO 2 / RCOOR/RH KCN form RCN while AgCN form RNC since KCN is ionic which provide CN but AgCN is covalent, therefore e - pair on N easily donated. (v) Elimination reaction: - When RX react with alc. KOH form alkene CH 3 CH 2 Cl + alc.KOH ------> CH 2 =CH 2 + KCl Saytzeff rule: - When assymetric alkylhalide react with alc.KOH form alkene major product is (which has more alkyl gp)
(vi) Reaction with metal: - Alkyl halide reacts with metal to form organo-metallic compound. I st such compound was formed by Victor Grignard called Grignard reagent. RX + Mg ----dry ether-------> RMgX which is very reactive. React with moisture to form alkane RMgX + H 2 O ---> RH + Mg(OH)X (vii) Wurtz reaction: - 2RX + Na ----dry ether----> R-R + 2NaX Fittig reaction 2C 6 H 5 X + 2Na ----> C 6 H 5 -C 6 H 5 + 2NaX Wurtz fittig reaction: - C 6 H 5 X + RX + 2Na -----> C 6 H 5 R + 2NaX 8. Chemical reactions of Haloarenes: - (i) Nucleophilic substitution reaction (ii) Electrophilic substitution reaction (iii) Reaction with metal (i) Nucleophilic substitution reaction: - Halo arenes doesnot give since (a) C-Cl is strong partial = bond (169pm but in RX C-Cl = 177pm) (b) phenyl cation is unstable due to resonance But under drastic condition (or in presence of e - withdrawing gp NO 2 ) give
(ii) Electrophilic substitution reaction: - give O, -P compound (a) Halogenation
(b) Nitration
(c) Sulphonation
(d) Friedel Craft alkylation/ acylation
(iii) Reaction with metal Fittig/ Wurtz Fittig reaction
9. Polyhalogen compounds (a) Dichloromethane CH 2 Cl:- used as solvent in paint remover/metal cleaning drugs but harmful to central nervous system. (b) Chloroform CHCl 3 :- used as solvent for fats, alkaloids, I 2 in Freon R-22, anaesthatics. Damage liver, react with O 2 to form poisonous gas phosgene CHCl 3 + O 2 -----light-------> 2COCl 2 + 2HCl (Carbonylchloride) Therefore, stored in dark, full bottle (Since no air) (c) Iodoform CHI 3 :- used as anaesthatic but give foul odour of I 2
(d) Carbon tetrachloride CCl 4 :- used as solvent, refrigerant, propellant, fire extinguisher but exposure causes liver cancer, nausea, vomiting, coma. (e) Freons chlorofluoro carbon CF 2 Cl 2 :- Used as propellents refrigerator, air conditioning, upset ozone layer. (f) D.D.T p,p-dichloro,diphenyl trichloro ethane Paul muller was awarded noble prize on it Used against mosquito and lice Highly toxic to fish 10. Mechanism of nucleophilic substitution reaction:- Stronger nucleophile replace weaker nucleophile in alkyl halide is called nucleophilic substitution reaction. Reaction proceed through two mechanism (a) S N 2 mechanism : - (i) rate depend on conc. Of two reactant (2 order) (ii) Reaction proceed through single step. Breaking of bond and incoming nucleophile take place simultaneously. (iii) Due to steric effect reactivity 1 0 >2 0 >3 0 / RI > RBr > RCl > RF (iv) Product has inverted configuration as compared to reactant :Nu attach on opposite side of halide
(b) S N 1 mechanism (i) Rate depend on conc. of one reactant (Ist order) (ii) Reaction proceed in two step formation of cation then cation react with nucleophile (iii) Reactivity 3 0 >2 0 >1 0 / RI > RBr > RCl > RF (iv) Give Product as recemic mixture. Since carbocation formed in slow step Therefore, :Nu may attach to either side ( may same configuration or inverted to reactant) (v) Require polar protic solvent (H 2 O, ROH, RCOOH) (vi) (CH 3 ) 3 -X ----slow---> (CH 3 ) 3 C + + X - (CH 3 ) 3 C + + :Nu --> (CH 3 ) 3 C-Nu: (Produce E) (vii) Allylic (CH 2 =CH-CH 2 X) & benzylic show high reactivity in S N 1
11. Stereochemical aspect of nucleophilic substitution reaction (i) Plane polarised light Light obtained through nicol prism (Calcite ore CaCO 3 ) is called plane polarised light. (ii) Optical activity :- When plane plorised light is passed through certain compound it rotated to right direction called dextro (d,+) and if rotated to left direction called leavo(l,-). These compounds are called optically active and the phenomenon is called optical activity. (iii) Asymmetric centre :- If all four substituent attached with C-atom are different then it is called asymmetric C-atom. Assymetry is responsible for optical activity. (iv) Chirality :- The objects which form non superimposable image on their mirror image is called chiral and the property is called chirality. Eg p, q, butane 2-ol, 2,3 dihydroxy propanal (v) Achirality :- Objects which form superimposable image on their mirror image is called achiral and the property is called achirality. Eg. Propan-2-ol (vi) Enantiomers: - Optical active isomers are called enantiomers (d and l) (vii) Recemic mixture: - Mixture of two enantiomers (d and l) in equal proportion have zero optical rotation is called racemic mixture (dl of +-) and the process is called recemisation. (viii) Retention: - Retention of configuration is, preservation of integrity of spatial arrangement of bond to asymmetric centre, during chemical reaction i.e product have same configuration.
(ix) Inversion: - If bond broken and configuration change during reaction is called inversion.