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C H 3— C H, , CH—CHO, , LiAlH, , 4, , , , , C H 3— C H, , H, , C H— C H 2— O H, , Crotonaldehyde, Ph—CH, , (e), , P h — C H 2— C H 2— C H 2— O H, , H / OH, , Cinnamaldehyde, From et her s :, dil.H SO, , R—O—R, , R—OH + R—OH, , 2, 4, , , , dil.H SO, , CH 3 —O—CH 2 CH 3, (f), , LiA lH, , 4, , , , , –, , CH—CHO, , CH 3 —OH + CH 3 CH 2 —OH, , 2, 4, , , , From acid a nd derivat ive s (By reduct ion) :, LiAlH, , R—COOH, , 4, , , , , R C Cl, , 4, , , , , R—CH 2 —OH + H 2 O, , H, , LiAlH, , R—CH 2 —OH + HCl, , H, , O, LiAlH, , 4, , , , , R C OR, , R—CH 2 —OH + R—OH, , H, , O, LiAlH, , 4, , R C O C OR , , , R—CH 2 —OH + R—CH 2 —OH, , H, , O, , O, LiAlH, , 4, , , , , R C NH2, (g), , R—CH 2 —NH 2 +H 2 O, , H, , O, From e ster s (By hydrolysis) :, (i), By alkali ne hydrolysis :, NaOH, , , , R C OR, , R C ONa + R OH, , O, (ii), , O, , By acidic, , hydrolysis :, , , H, , , , H O (excess) , , R C OR, , 2, , R C OH + R OH, , O, , O, , , 18, , H O, , 3, , , , , , CH3 C OC2H5, , 18, , CH3 C OH + C2H5OH, O, , O, , This reaction is reversible reaction and it's order is 1 and it is also called Pseudo-Unimolecular reaction., (h), From p-ami ne s :, R—NH2, , CH 3 CH 2 — N H 2, , , NaNO HCl, , 2, , , , or HNO 2, , HNO, , 2, , , , R—OH + N 2 + H 2 O, CH 3 CH 2 —OH + N 2 + H 2 O, , Mechanism :, , , , , , , , , NaNO 2 HCl, CH 3 CH 2 — NH 2 , CH 3 CH 2 — N 2 Cl CH 3 CH 2 N 2 Cl, , (Unstable)
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, , OH, , CH3CH2, , OH [major], , CH3CH2, , Cl, , , , Cl, , , , CH3CH2, , , , O, , N O, , CH3CH2 O N O, , , , H, , CH2 CH2, , Inter mediate is carbocation so rearrangement may be possible., Ex., , NaNO2 HCl, CH 3 CH 2 CH 2 —NH 2 , ?, , S o l . Mechanism :, , , NaNO 2 HCl, , , , CH 3 CH 2 CH 2 —N H 2, , , , , , CH 3 CH 2 CH 2, , CH 3 CH 2 CH 2 — N 2 Cl, , , , , , , HO, H, CH3 CH CH3, CH3 CH CH3, , OH, HNO 2, CH 3 — NH 2 , CH 3 — O — CH 3, , E x c e p t io n :, , (i), , From Grignard reagent :, (i), p-alcohol :, R—Mg—X + [O], , , , H2 O, , , , R—O—MgX, , R—OH, [Same C-p-alcohol], , R, , , , , R Mg, , R, , HO, X + H C H H C H H C H, 2, , O, , OMg X, , OH [one C more p-alcohol], , R, , , , , R Mg, , R, HO, , 2, CH2 CH2 CH2 , CH2 CH2, , X + CH2, , O, (ii), , OMgX, , OH, [two C more p-alcohol], , s-alcohol :, , R, R Mg, , X + R C H R, O, , R, H2O, , C H R, , C H, , OMgX, , OH, R, , R Mg, , R MgX, X + H C OR H C R , H C R, HO, 2, , O, , O, , OH
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(iii), , t-alcohol :, , R, R Mg, , R, HO, , 2, C R , R, , C R, , OMgX, , OH, , X + R C R R, O, , R, R Mg, , O, , , R MgX, C R R, , C R, , O, , OH, , X + R C OR R, , H2O, , Physical proper t ie s :, (i), , C1 to C11 are colourless liquids and high alcohols are solids., , (ii), , Density of monohydric alcohol is less than H2O., , (iii), , Density, , (iv), , Solubility : C 1 to C3 and t-butyl alcohol is completely soluble in H2O due to H–bonding., , mol. wt. (for monohydric alcohol)., , solubility No. of side chainsc, , 1, , molecular weight, , Order of solubi lit y :, C 4 H 9 OH, , >, , C 5 H 11 OH, , >, , C 6 H 13 OH, , CH3, CH 3 CH 2 CH 2 CH 2 OH, , <, , CH3CH2CH OH <, , CH3 C OH, CH3, , CH3, <, , CH3CHCH, 2, 2, , <, , CH3 CH CH2, , OH, , OH, , OH OH, [Number of —OH increases, H-bonding increases], (v), , CH2 CH CH2, OH OH, , Boiling points : B.P. molecular weignt, If molecular wt. is same then, , Order of BP :, , C 4 H 9 OH, , <, , B.P. , , 1, branching, , C 5 H 11 OH, , <, , C 6 H 13 OH, , CH3, CH 3 CH 2 CH 2 CH 2 OH, , >, , >, , CH3CH2CH OH, , CH3, , CH3, , CH3CHCH, 2, 2, , <, , <, , CH3 CH CH2, , OH, , Boiling point of alcohol is more than corresponding ether. Why ?, , S o l . Reason : H-bonding in alcohol., O H---------- O H------------- O H ------------- O H ---------R, , R, , R, , CH2 CH CH2, OH, , OH OH, [Number of OH increases, H-bonding increases], Ex., , CH3 C OH, , R, , OH OH
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Ex., , Boiling point of alcohol is less than corresponding carboxylic acid. Why ?, , S o l . Reason : Dimer formation in carboxylic acid., , O, R, , H O, , C, , C, OH, , , , R, , O, , Chemical proper t ie s :, Monohydric alcohol show following reactions, (A), , Reaction involving cleavage of O, , (B), , Reaction involving cleavage of C, , (C), (A), , H, , OH, Reaction involving complete molecule of alcohol, , Reaction involving cleavage of O, , H: Reactivity order (Acidic nature) is, , C H 3— O H, , >, , (CH 3 ) 2 CH—OH, , CH, , CH, , (i), , >, , C H3C H2—O H, , >, , (CH 3 ) 3 C—OH, , Acidic nature :, H 2O >, , R—OH, , >, , >, , NH 3 (Acidic strength), , Alcohols are less acidic than H2O and neutral for litmus paper and gives H2 with active metals (Na, K), , (ii), , R—OH + Na , , R—ONa +, , R—OH + K , , R—OK +, , 1, H, 2 2, 1, H, 2 2, , Reaction with CS 2 :, R—OH + Na, , , , R—ONa + S, , C, , S , , R—ONa +, R, , O, , 1, H, 2 2, , C, , S, , Na, , S, Sodium alkyl xanthate (Used as floating agent), (iii), , Alkylation:, R—OH, , CH 2 N 2 , , , , R—OH, , Na, , , , R — O — C H 2— H, R—ONa, , R X, , , , R—O—R, (Williamson synthesis), , (iv), , Acylation :, , R, , OH + Cl, , C, , R, , , , R, , O, , R, , OH + Cl, , C, , O, , C, , R, , O, (Acylation), CH3 , , R, , O, , C, , CH3, , O, , O, , (Acetylation), , O, , OH, COOH, Salicylic acid, , CH 2 COCl, , , , C, , R, , O, COOH, Acetoxy benzoic acid, Acetyl salicylic acid, Aspirin [Used as analgesic]
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(b), , Victor - Meyer test : This is colour test for alcohol (pri. sec. & tert.) ., p-alcohol, , Red colour, s-alcohol, , Blue colour, t-alcohol, , No colour, R—CH 2 —OH [1°], R 2 CH—OH [2°], , , , , , , , P + I2, , P + I2, , R — C H 2— I, , P + I2, , R 2C H — I, , R 3C — I, , , , , , , , AgNO2, , AgNO2, , R C H 2— N O 2, , AgNO2, , R 2C H — N O 2, , R 3C — N O 2, , , , , , , HNO2, , HNO2, , R—C—NO2, , No reaction, , , N, , , , , , NaOH, , NaOH, , Soluble (Red), (v ii) Dichromate te st :, 1° Alcohol, , HNO2, , R 2C — N O 2, , N OH, , Insoluble (Blue), , H K Cr O, , 2 2 7, , , , 6, , orange [Cr, , R 3 C—OH [3°], , NaOH, , Colourless (White), , Acid + Cr+3, , ], , [green], 2° Alcohol, , H K Cr O, , 2 2 7, , , , 6, , orange [Cr, , ], , Ketone + Cr +3, [green], , 3° Alcohol, , H K Cr O, , 2 2 7, , , No oxidation, No green, orange [Cr 6 ], , (v iii) Te st of alcholic group :, R—OH, , Na, , , , R—ONa +, , 1, H, 2 2, , [effervesence of H2], R—OH, , PCl 5, , , , R—Cl + POCl 3 + HCl, , NH 3, , NH 4Cl, , [White fumes], Cerric ammonium nitrate, Red colour, , , Distinction between CH3 – OH and C 2 H 5 OH, , R—OH, , (ix), , C H 3O H, , C H 3C H 2O H, , B.P., , 65°C, , 78°C, , I 2 + NaOH, , No ppt, , Yellow ppt of CHI3, , Cu/300°C, , Smell of formalin [HCHO], , No smell, , Salicylic acid, , Smell of oil of wintergreen, , No smell
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(a), , Middle oil fraction of coaltar:, , Fractional, Coaltar , Middle oil (170-230°), distillation, , (Phenol, cresols, Naphthalene), , Coal, , Naphthalene, (Solid crystals separate out), , liquid, NaOH (dil.), , C6HONa, 5, CO2/H2O or sulphuric acid, , C6HOH, + Na2CO3, 5, (b), , From cumene (Isopropyl benzene) : Cumene is oxidised with oxygen into cumene hydroperoxide in, presence of a catalyst. This is decomposed by dil. H2SO4 into phenol and acetone., , CH3, , O OH, , CH3, , C(CH3)2, , CH, , (c), , + CH3 C CH3, , H SO ,H O, , O, , 2, 4, 2, , , H / 100 C, , 2, , , 130 C, , Cumene, , OH, , O, , Cumene hydroperoxide, , o, , Raschig process : Chlorobenzene is formed by the interaction of benzene, HCl and air at 300 C in, o, , presence of catalyst CuCl2 + FeCl3. It is hydrolysed by superheated steam at 425 C to form phenol and, HCl., C6H6 + HCl +, , 1, O, 2 2, , CuCl, , FeCl, , 2, 3, , , 0, , 300 C, 0, , C 6H 5 Cl + H 2 O, , 425 C, , , , C 6H 5 Cl + H 2 O, C 6 H 5 OH + HCl, , (super heated steam), (d), , Dow process : This process involves alkaline hydrolysis of chloro benzene-(large quantities of phenol, formed)., OH, C 6 H 5 Cl + NaOH, , , , Cu — Fe, , , , 300 0 C, , + NaCl, , Physical proper t ie s :, (i), (ii), , Phenol is a colourless, hygroscopic crystalline solid., It attains pink colour on exposure to air and light. (slow oxidation), C 6H 5OH-------- O, , (iii), (iv), (v), (vi), , O----------- HOC 6H 5, , Phenoquinone(pink colour), It is poisonous in nature but acts as antiseptic and disinfectant., Phenol is slightly soluble in water , readily soluble in organic solvents., Solublity of phenol in water is much lower than alcohols because of larger hydrocarbon part in the, molecule., Due to intermolecular H-Bonding, phenol has relatively high boiling point than the corresponding, hydrocarbons, aryl halides etc. but intermolecular H-bonding in o–derivatives is used in the preparation, of dyes, drugs, bakelite and it's melting point (MP) is 43° C and boiling point (BP) is 182° C .
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, , Chemical Proper t ie s :, , (A), , React ions due to, , , –OH group :, , Acidic Nature : Phenol is a weak acid. The acidic nature of phenol due to formation of stable phenoxide, ion in solution. The phenoxide ion is stable due to resonance. The negative charge is spread through out, the benzene ring which is stabilising factor in the phenoxide ion. Electron withdrawing groups, (–NO 2, –Cl) increase the acidity of phenol while electron releasing groups (–CH 3 etc.) decrease the, acidity of phenol., , , , , , , , C6H5 O H3O, , C 6 H 5 OH, , Phenol is stronger acid than alcohols but weaker than the carboxylic acids and even carbonic acid, The acidic nature of phenol is observed in the following:, (i), , Phenol changes blue litmas to red., , (ii), , Highly electro positive metals react with phenol., 2C 6 H 5 OH + 2Na , , (iii), , 2C 6 H 5 ONa + H 2, , Phenol reacts with strong alkalies to form phenoxides., , , C 6 H 5 OH NaOH , (iv), , C 6 H 5 O N a H 2 O, , However phenol does not decompose Na2CO3 or NaHCO3 because phenol is weaker than carbonic acid., C 6 H 5 OH + Na 2CO 3 or NaHCO 3, Ph—OH, , +, , Acid-I, , Acid-I, Base-I, (v), , <, <, , , , No reaction, , NaHCO3, , Ph—ONa, , Base-I, , Base-II, , +, , H 2 CO 3, Acid-II, , Acid-II, Reaction in reverse direction., Base-II, , Phenol does not react with NaHCO3., , CH3 C OH, , +, , NaHCO 3, , CH3 C ONa, , O, , H 2 CO 3 [H 2O + CO 2 ], , O, , Acid-I, , Acid-I, Base-I, , +, , >, >, , Base-I, , Base-II, , Acid-II, , Acid-II, Reaction in forward direction., Base-II, , (vi), , Acetic acid reacts with NaHCO3 and gives effervesence of CO2., , , , Reaction with PCl 5 : Phenol reacts with PCl 5 to form chloro benzene. The yield of chlorobenzene is, poor and mainly triphenyl phosphate is formed., C 6H 5 OH + PCl 5, , , , 3C 6 H 5 OH + POCl 3, , , C 6H 5Cl + POCl 3 + HCl, , , , (C 6H 5) 3 PO 4 + 3HCl, , Reaction with Zn dust: When phenol is distilled with zinc dust benzene is obtained., C 6 H 5 OH + Zn, , CH2 OH, Ex., S o l . No reaction, , Zn, , ?, , , , C 6 H 6 + ZnO
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CH3, OH, , Ex., , Zn, , ?, , CH3, Sol., , CH3, CH3, , Ex., , Zn, , ?, , S o l . No reaction, , COOH, OH, , Ex., , Zn, , ?, , COOH, Sol., , , , Reaction with NH 3 ( Bucherer reaction): Phenol reacts with NH 3 in presence of anhydrous ZnCl 2 to, form aniline., C 6 H 5 OH + NH 3, , , , Anhydrous ZnCl or (NH ) SO / NH 150 C, , 2, 4 2, 3, 3, , , , 300 C, , C 6 H 5 NH 2 + H 2 O, , Reaction with FeCl 3 : Phenol gives violet colouration with FeCl3 solution (neutral) due to formation of a, complex., C 6H 5 OH + FeCl 3 , , Voilet colour, , This reaction is used to differentiate phenol from alcohols., , , Acetylation (Schot ten-Baumann reaction) : Phenol reacts with acid chlorides or acid anhydrides in, alkali solution to form phenyl esters., C 6 H 5 OH + ClCOCH 3, , NaOH, , , HCl, , C6H5O—C CH3, O, , C6HOH, + Cl, 5, , , , NaOH, , C C6H5 , HCl, , C6H5O, , C—C6H5, , O, O, Ether formation (Alkylation) : Phenol reacts with alkyl halides in alkali solution to form phenyl ethers., (Williamson's synthesis), C 6 H 5 OH + NaOH, , alkali solution, , , , RX, C 6 H 5ONa , NaX C 6 H 5 OR, , Sodium phenoxide, , , , C 6 H 5 OH + CH 2 N 2, , , , Reaction with P 2 S 5 :, , 5C 6 H 5 OH + P 2 S 5, , C 6H 5OCH 3 + N 2 , , , , 5C 6 H 5 SH + P 2 O 5
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, , Hydrogenation: Phenol when hydrogenated in presence of Ni at 150-200 0C forms cyclohexanol., , OH, , OH, Ni, , + 3H2 , 150 – 200° C, , Cyclohexanol. (C6H11OH), (used as a good solvent), , , Frie s rear ra ngement react ion :, Anhydrous AlCl 3, C 6 H 5 OH + CH 3COCl , C 6 H 5 OCOCH 3, , OH, 60°C, , COCH3, , anhydrous AlCl, C6H5OCOCH3 , 3, , OH, , Phenyl ester (acetate), , , , COCH3, , Duff 's reaction: This method gives only the o-compound which is hindered by the presence of a –I, group in the ring., , OH, , OH, CH NCH3 H O, , , Glycerol, , +(CH), 2 6N4 , , , , CHO, , 2, , Boric acid, , Hexamethylene tetramine, , OH, , acidified with HSO, 2, 4, and steam distilled (15–20°C), , Coupling reactions: Phenol couples with benzene diazonium chloride in presence of an alkaline, solution to form a dye (p- hydroxy azobenzene) red only., , N2Cl +, , NaOH, , OH , –HCl, , N N, , OH, , p–hydroxy azobenzene (Orange dye or Red dye), Phenol couples with phthalic anhydride in presence of conc. H2SO4 to form a dye (phenolphthalien), used as an indicator., , O, O C C OH, +, H, Phenol (2 molecules), , , , O, OH, , H SO, , O C C, , 2, 4, , , OH, , –H2O, , OH, OH, , Phenolphthalien (Colourless in acidic, medium and pink in alkaline medium), , Lederer Manasse (Condensation w ith formaldehyde) : Phenol condenses with HCHO (excess) in, presence of NaOH or weak acid (H+) to form a polymer known as bakelite (aresin).
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ETHER, R—O—R (Dialkyl ether), alkoxy alkane. It's General formula is C n H 2n, , + 2 O., , CH 3 —O—CH 2 CH 3 (Methoxy ethane) or ethyl methyl ether or 2–oxa butane, Ether is monoalkyl derivative of R–OH and dialkyl derivative of H 2 O, H, , R , , R—OH, , R—O—R, , 2H, , 2R , , H—O—H, , Classification : They may be classified as :, (a), , Simple or symmetrical ether. e.g. R–O–R, , (b), , Mixed or unsymmetrical ether e.g. R–O–R', , Str ucture :, , : O : sp3 hybridized, , The molecule of ether is bent due to lone pair of electron on oxygen, atom- bond electron repulsion. The bond angle is 1100. It is greater, than that of water 1050 due to the repulsion between bulky alkyl groups., , 110°, , bond , R, , bond, R, , Due to bent structure, it posses dipole moment and hence are polar, molecules., , , , General Met ho ds of Preparat ion :, , (A), , From alkyl halide s :, (i), , By Williamson's synthesis :, R—X + Na—O—R, , , , Example : CH 3 —I + C 2 H 5 O – Na + , , R—O—R + NaX [ S N 2 Reaction], CH 3 —CH 2 O—CH 3 + NaI, , Mechanism : [ S N 2 Reaction], , , , , , C2H5ONa, , C2H5O + Na, , H H, , H H, C2H5O, , Slow, , C— I, , C2H5O------ C ----- I, , , , NaI, , CH3, Example :, , C2H5—O—CH3+ I, , H, , H, Na + I, , Fast, , CH3, , C, , CH2, Cl + CH3ONa H3C C, , CH3, , CH3, , CH3, Example : CH3, , C, , CH3, ONa + CH3, , CH2, , Cl, , , , , CH3, Example : CH 2, , CH—Cl + CH 3 CH 2 —ONa, , [Stable by Resonance], , CH3, , C, , O CH2, , CH3, , , No reaction, , CH3
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(ii), , Reaction with Dry Ag 2 O :, , , , 2RX + Ag 2 O, , R—O—R + 2AgX, , , Example : 2CH 3 —CH 2 —Cl + Ag 2 O , , (B), , From R–OH:, (i), , By dehydration :, , CH3CH2 O, , CH2CH3, , R—OH, , Con. H 2 SO 4, , ?, , , 250°C, , 140°C, Al2O3, , CH3, , CH2, , (ii), , CH2, , Ex., , CH2, , conc. H2SO4, , OH, , 350°C, , 170°C, , CH3CH2 O CH2CH3, (Willomson's synthesis), CH2 CH2, (Elimination), , Reaction with CH 2 N 2 (diazomethane) :, R—OH + CH 2 —N 2, , , , CH 3 CH 2 OCH 2 CH 3 + 2AgCl, , , , BF , 3, , R—O—CH 2 —H + N 2, , Physical Proper t ie s :, (i), , CH 3 OCH 3 , CH 3OCH 2 CH 3 are gases and higher are volatile liquids., , (ii), , Ether are less polar [=1.18D]., , (iii), , Ethers are less soluble in H 2 O., , (iv), , Ethers have less BP then corresponding alcohol., , Ethers are less soluble in H 2 O . Why ?, , S o l . Reason : Due to less polar, it forms weaker H–Bonding with H 2 O., Ex., , Ethers have less BP then corresponding alcohol. Why ?, , S o l . Reason : No, , , , H–Bonding in ether molecules., , Chemical proper t ie s :, Ethers are less polar so less reactive and do not react with active metals [Na,K], cold dil. acid, oxidising and, reducing agent., Reason : They do not have any active functional group., , 1., , Basic nature : Due to presence of .p on oxygen atom ether behave as lewis base, Ethers react with cold conc. acid and form oxonium ion, , .., cold ; conc. HCl, , C2H5, Example : C2HOC, 5.., 2H5, , , , O C2H5 Cl, , (diethyl oxonium chloride), , H, .., cold ; conc., C2H5, Example : C2H5 O, .. C2H5 , H SO, 2, , 4, , , , , , O C2H5 HSO4, H, , Ether form dative bond with Lewis acids like BF 3, AlCl 3 , RMgX etc., , (diethyl oxonium hydrogen sulphate)
