(1) Alkyl halides can be prepared by several methods including the reaction of alcohols with hydrogen halides or phosphorus halides, direct halogenation of hydrocarbons, halide exchange, addition of hydrogen halides to alkenes, and from silver salts of carboxylic acids. (2) Alkyl halides are usually liquids with higher boiling points than alkanes due to their polarity. (3) Alkyl halides undergo nucleophilic substitution reactions to form organometallic compounds and can be reduced to alkanes. They also undergo elimination reactions and dehydrohalogenation. (4) Dihalogen and trihalogen derivatives include compounds like
(1) Alkyl halides can be prepared by several methods including the reaction of alcohols with hydrogen halides or phosphorus halides, direct halogenation of hydrocarbons, halide exchange, addition of hydrogen halides to alkenes, and from silver salts of carboxylic acids. (2) Alkyl halides are usually liquids with higher boiling points than alkanes due to their polarity. (3) Alkyl halides undergo nucleophilic substitution reactions to form organometallic compounds and can be reduced to alkanes. They also undergo elimination reactions and dehydrohalogenation. (4) Dihalogen and trihalogen derivatives include compounds like
(1) Alkyl halides can be prepared by several methods including the reaction of alcohols with hydrogen halides or phosphorus halides, direct halogenation of hydrocarbons, halide exchange, addition of hydrogen halides to alkenes, and from silver salts of carboxylic acids. (2) Alkyl halides are usually liquids with higher boiling points than alkanes due to their polarity. (3) Alkyl halides undergo nucleophilic substitution reactions to form organometallic compounds and can be reduced to alkanes. They also undergo elimination reactions and dehydrohalogenation. (4) Dihalogen and trihalogen derivatives include compounds like
(1) Alkyl halides can be prepared by several methods including the reaction of alcohols with hydrogen halides or phosphorus halides, direct halogenation of hydrocarbons, halide exchange, addition of hydrogen halides to alkenes, and from silver salts of carboxylic acids. (2) Alkyl halides are usually liquids with higher boiling points than alkanes due to their polarity. (3) Alkyl halides undergo nucleophilic substitution reactions to form organometallic compounds and can be reduced to alkanes. They also undergo elimination reactions and dehydrohalogenation. (4) Dihalogen and trihalogen derivatives include compounds like
(I) From Alcohols (a) By using hydrogen halide R OH HX RX + H2O (b) By using phosphorous halides ROH + PCl5 RCl + POCl3 + HCl 3ROH + PCl3 3RCl + H3PO3 3ROH + PBr3 3RBr + H3PO3 3ROH + PI3 3R I + H3PO3 (c) By using SOCl2 (thionyl chloride) R OH + SOCl2 R Pyridine Cl + SO2 + HCl
(II) By Direct halogenation of hydrocarbons
RH X 2 R X + HX h
Reactivity of hydrocarbon in the above reaction with respect
to type of hydrogen to be replaced follows following order
1 Tertiary hydrogen > Secondary hydrogen > Primary hydrogen. (III) By halide Exchange R Cl NaI R I + NaCl Aceton e
R Br NaI R I + NaBr Acetone
(IV) By addition of HX to alkenes
Alkyl chlorides, bromides and iodides can be prepared by treating an alkene with corresponding hydrogen halides (HCl, HBr and HI). The addition of these compounds to alkene takes place according to Markovnikov's rule.
(V) From silver salts of carboxylic Acid
CCl RCOOAg + X2 4 RX + AgX + CO2 (X2 = Cl2 or Br2) This reaction is popularly known as Hunsdieker reaction.
(VI) Preparation of allylic or benzylic halides
(i) Direct halogenation of any aromatic hydrocarbon preferably gives benzylic halide. This is because benzyl radical is resonance stabilized.
2 CH2 CH3 X CH CH3 X 2
h
(VII) Preparation of Polyhalides
Addition of halogen (Cl2 or Br2) to alkynes produces tetrahaloderivatives. X X | | HC CH X2 CH = CH X2 HCCH | | | | X X X X
(VIII) Preparation of Vinyl halides
CH CH HCl CH2 = CH CuCl 2 | Cl
PHYSICAL PROPERTIES Because of small polarity in alkyl halides (carbonhalogen bond is polar due to difference in electronegativities of the two atoms) as well as greater molecular weights, alkyl halides have considerably higher boiling points than alkanes containing same number of carbon atoms.
CHEMICAL PROPERTIES (I) Preparation of Organometallic compounds 3 RX Mg RMgX ether
(Grignard reagent) RX Li R Li + LiX ether
(Organo lithium compound)
(II) Reduction of alkyl halides
RX Reduction RH The reagents used for reduction of alkyl halide to alkane are Zn and CH3COOH, Zn and HCl, Zn and NaOH, Zn Cu couple and alcohol, aluminium amalgam and alcohol etc.
(III) Wurtz reaction
2R X + 2Na ether R R + 2NaX Details about this reaction had already been discussed during preparation of alkanes. (IV) Dehydrohalogenation of alkyl halides RX alcoholic KOH Alkene
More substituted alkene is always obtained as a major
product.
Dihalogen Derivatives Two halogens may be linked to the same or different carbon atoms. Cl Cl H Cl H C C H or Cl CH2CH2 Cl H C C Cl or CH3CHCl2 H H H H ethylene chloride ethylidene chloride (1,2 or vicdichloroethane) (1,1 or gemdibromoethane)
Methods of Preparation (i) By the action of phosphorus pentahalides on aldehydes or ketones (ii) By the addition of halogen halides to alkynes (iii) By the addition of halogens to alkenes (iv) By the action of hydrogen halides or phosphorus halides on glycols.
5 Physical Properties (i) They are sweet smelling colourless liquids, having comparatively high boiling point. Highest members are solids. (ii) They are in general heavier than water. Methylene iodide is the densest organic liquid known, its density being 3.325. (iii) They are insoluble in water and soluble in organic solvents.
Chemical Properties Chemically the dihalides are similar to monohalogen derivatives giving all the reactions of the halogen atom in duplicate. They however, differ from the latter in certain reactions in which both the halogens are involved together. Besides the usual reactions of alkyl halides, they give the following typical reactions.
6 (i) Hydrolysis with aqueous alkalies: 1,2dihalides upon heating with aqueous KOH give the respective glycols. Thus, CH2 Cl CH2 OH + 2KOH + 2K+Cl CH2 Cl CH2 OH ethylene ethylene chloride glycol
(ii) Dehalogenation with zinc dust and methanol: When
treated with zinc dust and methanol, 1,1dihalides eliminate a molecule of halogen, giving alkenes. Thus, H Br CH3CH2 C + Zn ZnBr2 + CH3CH = CH2 propene Br 1,1dibromopropane
(iii) Dehydrohalogenation with ethanolic KOH: Both
1,1dihalides and 1,2dihalides when heated with ethanolic potassium hydroxide, give alkynes. Thus, H Cl H C C H + 2KOH ethanol H C C H + 2KCl + 2H2O acetylene H Cl ethylene chloride (1,1dihalide)
7 The name chloroform was given to trichlormethane by Dumas who established that its molecule contained chlorine in union with ‘formyl’ an old name for CH group. Preparation (i) By heating ethanol or acetone with bleaching powder, Ca(ClO)Cl: The bleaching powder provides chlorine and the reaction takes place in three stages. Thus the formation of chloroform from ethanol occurs as follows. (a) Oxidation of ethanol to acetaldehyde CH3 CH2OH + Cl2 CH3 CHO + 2HCl ethanol acetaldehyde (b) Chlorination of acetaldehyde to chloral CH3 CHO + 3Cl2 CCl3 CHO + 3HCl chloral (c) Hydrolysis is of chloral by lime present in bleaching powder to form calcium formate and chloroform. CCl3 CHO + HOH CHCl3 + HCOOH chloroform formic acid 2HCOOH + Ca(OH)2 (HCOO)2Ca2+ + 2H2O
8 With acetone as the starting material, the conversion into chloroform takes place by similar steps. CH3 CO CH3 + 3Cl2 CCl3 CO CH2 + 3HCl acetone trichloroacetaone CCl3 CO CH3 + HOH CHCl3 + CH3COOH acetic acid
Physical Properties Chloroform is colourless liquid having a peculiar sickly smell and a sweetish burning taste, boiling point 61°C, sp gr 1.485. It is practically insoluble in water but soluble in most organic solvents. It acts as a solvent for many organic substances such as oils, fats and waxes. Chloroform vapour when inhalded causes temporary unconsciousness and hence its use as anaesthetic.
Chemical Properties (i) Oxidation:
9 (a) In the presence of light, chloroform is oxidized slowly by the oxygen of air to form carbonyl chloride or phosgene. (b) Fehling solution oxidizes chloroform when a red deposit of copper (I) oxide is produced. (c) It is not inflammable but when a Bunsen burner is played on to the liquid chloroform it vaporizes and burns with a greenedged flame.
(ii) Reduction: Nascent hydrogen generated by the action of
zinc on ethanolic hydrogen chloride, reduces chloroform to dichloromethane. (iii) Hydrolysis with alkali: When treated with hot solution of NaOH (or KOH), chloroform is hydrolysed to form sodium chloride (or potassium chloride) and sodium formate or potassium formate. (iv) Nitration: It reacts with concentrated nitric acid to form chloropicrin or mononition chloroform (boiling point = 120°C). Chloropicrin is used as insecticide and also as a war gas. (v) Carbylamine Reaction (Isocyanide Reaction): Chloroform when warmed with an ethanolic solution of potassium hydroxide, forms an isonitrile (carbylamine).
10 Isonitriles have characteristic powerful and unpleasant smell and their formation of sometimes used as a delicate test for primary amines. (vi) Dehalogenation: When warmed with silver powder, chloroform gives acetylene. (vii) Condensation with Acetone: Chloroform undergoes condensation with acetone in the presence of alkali to form chloretone which is used as hypnotic. (viii)Action with Phenol and Sodium hydroxide (Reimer Tiemann Reaction): When heated with concentrated solution of KOH, chloroform gives salicylaldehyde.
Uses (i) Chloroform can be used to some extent as an anesthetic, solvent and reagent. (ii) Tricholromethane is used as solvent for iodine and fats. (iii) Chloroform is used in the manufacture of freezing refrigerant. Tetra-halogen Derivatives Carbon Tetrachloride, Tetra-chloromethane, CCl4 Preparation: It is prepared on industrial scale (i) By chlorination of methane:
11 CH4 + 4Cl2 CCl4 + 4HCl (ii) By the action of chlorine on carbon disulphide (CS2) in the presence of aluminium chloride as a catalyst. CS2 + 3Cl2 AlCl 3 CCl4 + S2Cl2sulphur monochloride The products of this reaction, both liquids, are separated by fractional distillation.
Physical Properties Carbon tetrachloride is a colourless liquid, boiling point 77°C. It is insoluble in water but soluble in all organic solvents. It is an excellent solvent for fatty substances.
Chemical Properties Carbon tetrachloride is relatively inert substance. It gives following reactions. (i) Action with Steam: Its vapours when mixed with steam react at high temperature to give phosgene gas. (ii) Action with Alkalis: When boiled with ethanolic KOH soution, carbon tetrachloride is hydrolysed to form potassium carbonate.
12 (iii) Reduction: Carbon tetrachloride canbe reduced by moist iron fillings to chloroform. This is an industrial method for the preparation of chloroform. (iv) Action with HF: When hydrogen fluoride is passed into carbon tetrachloride in presene of antimony pentachloride, the gas dichlorofluoromethane is obtained. This gas (freon) is widely used as operating fluid for refrigerators and in airconditioning equipment.
ARYL HALIDES Aryl halides are halogen compounds directly linked to a fragrant ring. The general formula of aryl halides is ArX, where Ar is phenyl, substituted phenyl or aryl groups.
METHODS OF PREPARATION OF ARYL HALIDES
(I) From Diazonium Salts BF4 , C6H5F CuCl, HNO 3 HONO C6H5Cl C6H5NO2 C6H5NH2 C6H6 C6H5N2 redn . + H 2 SO 4 Sn / HCl 0 C CuBr, C6H5Br
I , C6H5I
13 (II) By Halogenation of Arenes or Substituted Arenes Lewis acid ArH + X2 ArX + HX where X2 = Cl2 or Br2 Lewis acid = FeCl3, AlCl3, Tl (OAc)3 etc.
GENERAL CHEMICAL PROPERTIES OF THE ARYL
HALIDES Low reactivity of aryl and vinyl halides An alkyl halide is conveniently detected by the precipitation of insoluble silver halides when it is warmed with alcoholic AgNO3. Ag+
X OH
Aryl Halide OR
No reaction under or NH3 normal conditions.
C=CX CN
Vinyl Halide ArH,
AlCl3
The typical reaction of alkyl halides, is nucleophilic
substitution.
14 R X +:Z R Z + :X Where Z = OH, OR, NH3, CN, NH2 , ROH, H2O etc.
(I) Formation of Grignard Reagent
dry ether ArBr + Mg ArMgBr
tetrahydrofuran ArCl + Mg ArMgCl
(II) Electrophilic Aromatic Substitution
Although halogen is deactivating but still it directs the incoming electrophile to ortho and para position. For example, (i) Nitration Cl Cl Cl NO2 + HNO3 H SO 4 2 +
DDT is prepared by heating chlorbenzene and chloral with concentrated sulphuric acid
Cl H Cl H 2 SO 4 CCl3CH CCl3CHO + H 2O
H Cl Cl
1,1,1trichloro2,2 bis (pchlorophenyl) ethane or DDT
DDT is a solid compound, melting point is 109110°C.
Benzene Hexachloride (BHC)
1,2,3,4,5,6hexachlorocyclohexane, can theoretically exist in nine stereoisomeric forms due to different arrangements of H and Cl on opposite sides of the plane of benzene ring 16
