1. INTRODUCTION 2. TYPES OF POLYNUCLEAR HYDROCARBONS 3. NAPHTHALENE 4. SYNTHESIS OF NAPHTHALENE 5. CHEMICAL REACTIONS OF NAPHTHALENE 6. MEDICINAL USES OF NAPHTHALENE 7. DERIVATIVES OF NAPHTHALENE QO) INTRODUCTION * The class of aromatic hydrocarbons containing multiple aromatic rings in which the electrons are delocalized are known as polynuclear hydrocarbons. Examples of polynuclear hydrocarbons: 1. Simplest polycyclic aromatic hydrocarbons, e.g., benzocyclopropene (C,H), benzocyclopropane (C;H,), benzocyclobutadiene (C,H,), benzocyclobutene (C,Hg), corannulene (C9H;), etc. 2. Linearly fused rings, e.g., naphthalene (two fused rings), anthracene (three fused rings), tetracene (four fused rings), pentacene (five fused rings), etc. | | 3. Non-linearly fused rings, e.g., phenanthrene, helicenes, triphenylene, etc. * The carbon skeleton of hydrocarbons like phenanthrene is also present in natural products such as steroids.Q) TYPES OF POLYNUCLEAR HYDROCARBONS > Polynuclear hydrocarbons can be grouped under two categories: | 1, Isolated Ring Compounds: These are polycyclic compounds in which | aromatic rings are isolated, e.g., dimethyl, triphenyl methane, p- terphenyl, diphenyl methane Triphenyl methane (ADK? <) H p-Terphenyl Diphenyl methane Diphenyl or Bipheny! 2. Fused Ring Compounds: * These are polycyclic compounds, in which aromatic rings are fused, ie., fused rings share one or more carbon atoms pairs. * These compounds are also named as condensed polynuclear hydrocarbons, e.g., naphthalene, anthracene, phenanthrene, etc. Naphthalene Anthracene Phenanthrene * Coal tar consists of all the three fused ring compounds (naphthalene, anthracene, and phenanthrene), with the percentage of naphthalene | (around 6%) being the highest.Q NAPHTHALENE + Naphthalene is a crystalline, aromatic, white, solid hydrocarbon having two fused benzene rings, with molecular formula C, Hg. * Naphthalene is also known as naphthalin or antimite. * Itis insoluble in water but soluble in organic solvent like alcohol, ether and benzene. Naphthalene * The monosubstituted naphthalenes are named using Greek letters a and B whereas polysubstituted naphthalenes are named using Arabic numerals for e.g. cs cote oh a-Naphthol f-Naphthol 1,8-Dibromo- 1 Methyl - naphthalene nitronaphthalene () SYNTHESIS OF NAPHTHALENE > Naphthalene can be prepared by the following methods: 1, From Coal Tar * Coal tar is the main source of naphthalene. * Decalin (decahydronaphthalene) in the presence of a metallic catalyst at 180°C undergoes dehydrogenation reaction to form naphthalene. Decalin2. From Diel's-Alder Reaction + Furan and benzyne reacts to form the Diels-Alder adduct * However, the reactions of Diels-Alder adduct of furan and benzyne in the presence of H2/Ni produces naphthalene. Furan Benzyne D.A. Adduct Naththalene 3. Haworth's Synthesis * Haworth's synthesis of naphthalene involves four types of reactions as follows: i. Friedel-Crafts acylation of benzene, ii. Clemmensen's reduction, iii. Ring closure, and iv. Aromatization Friedel-Crafts acylation of benzene Friedel-Crafts HOC Benzene succinic anhydride p-Benzoyl propionic acid oO Clemmensen's reduction Nc, bu, HO,C” Clemmensen's Reduction Zn-Hg/HCI 3-Benzoyl propanoic acid 4-Phenylbutanoic acidRing Closure it) ——————> + 1,0 Conc. H,S0, or PPA H0,€ Phenylbutyric oO acid a-Tetralone Aromatisation in) Zn Up/UC Pd Cor Se + 2H, Clemmensen's (Aromatisation) Reduction Sad > Naphthalene 1-Nitronaphthalene 1-Naphthylamine 1-Naphthol [ros a 1-Chloronaphthalene (ii) Halogenation: CU 1-Bromonaphthalene Naphthalene cl, Cl Fe cl 1-Chloronaphthalene(iii) Friedel-Crafts Alkylation AlCl; 1-Methylnaphthalene 2-Methyinaphthalene (Major) (Minor) Hs AlCl; 2-EthyInaphthalene CHCOCI, AICI, CS, (Non polar solvent) Methyl-1-Naphthyl Ketone COCH Naphthalene CH3COCI, AIC C,HsNO, (Polar solvent) — Methyl-2-Naphthyl Ketone(v) Sulfonation: Naphthalene-1-Sulfonic acid CO So3H Naphthalene >120°C CU Naphthalene-2-Sulfonic acid QU) MEDICINAL USES OF NAPHTHALENE | In production of phthalic anhydride. In the synthesis of dyes. Carbaryl drugs containing naphthalene moiety is an insecticide. Nadoxolol drug is used as an beta-blocker. Sulfonated naphthalene is used as surfactants. Amino naphthalene sulfonic acid is used in synthesis of synthetic dyes. The tetrahydronaphthalene and decahydronaphthalene are red as low volatility solvent. Naphthalene sulfonic acids are used to make plasticizers, dispersants in synthetic and natural rubbers, tanning agents in leather industries and in agricultural formulations. 9. Molten naphthalene is used to solubilize the poorly soluble aromatic compounds. 10. In household naphthalene is used as fumigant. 11. Naphthalene and its alkyl homologs are used for formation of creosol (carbon aceous chemicals) which is used as antiseptic and preservatives. 12. Naphthalene is used in production of polyethylene naphthalene for making plastic beer bottles. 13. Naphthalene is also used in veterinary medicine in dusting powders and internally as an intestinal antiseptic and vermicide. 14. Naphthalene drugs acts well in curing the cough, urine infection, eyes trouble and fever. ot) Sy Te ean) SI = 7 |(Q DERIVATIVES OF NAPHTHALENE > The derivatives of Naphthalene are Naphthols, Naphthylamines, Naphthoic acids, and Naphthoquinones NAPHTHOLS “ 1-Naphthol a-Naphthol USES: 1. It is used as a precursor for drug synthesis. 2. It is the main ingredient of Molisch reagent. 3. It is also used for the synthesis of dyes. * 2-Naphthol B-Naphthol USES: 1. It is used as an antiseptic for skin diseases. 2. Methyl and ethyl ethers of 2-naphthol such as nerolins are used in perfume industries. 3. It is also used for synthesizing dyes.NAPHTHYLAMINES | 2-Naphthylamine 1-Naphthylamine NAPHTHOIC ACIDS COOH COOH 1-Naphthoic acid 2-Naphthoic acid NAPHTHOQUINONES oty 1,2-Naphthoquinone 1,4-Naphthoquinone oO oO | . 2,6-Naphthoquinone1. INTRODUCTION 2. METHOD OF PREPARATION 3. CHEMICAL PROPERTIES 4. USE’S OF ANTHRACENE | Q) ANTHRACENE * Anthracene is a three-fused benzene ring solid polycyclic aromatic hydrocarbon (PAH) with the formula C,,H,o. * It's a substance found in coal tar. 8 9 3 . OO 5 10 4 CQ) METHOD OF PREPARTAION 1. Friedel craft reaction: Anthracene is prepared by condensation of two molecule of benzoyl chloride in presence of AICI, we COCO 2 -—_—__ -2HCI Benzyl chloride Anthracene| 2. Anthracene is also formed by reaction of benzene with 1,1,2,2- | tetramethane in presence of AICI, H ©: ook 8 COICO Anthracene N | | | | 3. Haworth synthesis : Benzene reacts with pthalic anhydride in the presence of AICI, to yield o-benzoyl benzoic acid, which upon reaction Conc. to 9,10-Anthraquinone. oO ZF AlCl, ) O-cp =o oO 0 Benzene phthalic anhydride 9,10-Anthraquinone Anthracene 4. Elbs reaction: Anthracene is prepared by pyrolysis of o-Methyl benzophenone 2-Benzoyl benzoic acid Anthracene 5. Diels elder reaction oO wy + CH) ==CH S CH= ci 14-naphthaquinone Buta-1,3-dlene fe coon 3 oO Zn dust I N Littl | NN Anthracene oOQO) CHEMICAL REACTION «* ELECTROPHILIC SUBSTITUION REACTION x X2/CS2 9-Haloanthracene Z $03H NO, 9-Nitroanthracene (CH3CO),0 ~ P| COCH; CH;COCI, AICl; ~ Anthracene Non polar solvent) CO Z 9-Acetylanthracene COCH3 CH,COCI, AlCl, (Polar solvent) 1-Acetylanthracene HO;S A SO High Ag Temp. Acetylanthracene-2,7-disulfonic acid Low $03H —S03H 2 Anthracene-2,7-disulfonic acid Electrophillic reactions of anthracene is concluded that nitration, halogenation, and Friedel-Crafts acylation in non polar solvent occurs at C9 position whereas in case of polar solvent Friedel-Crafts acylation occurs at C1 position. Temp. S Se S03H 2a * Bre“* REDUCTION Anthracene when reduced with sodium and isopentanol give 9,10- | dihydro anthracene upon further treatment with conc. H,SO, it gives back anthracene Na/Isopentanol Conc. Tone 1,50, “* OXIDATION acid to yield 9,10-anthraquinone a COO == CLIO acon | | + Anthracene undergoes react with sodium dichromate and sulphuric “+ DIELS-ALDER REACTION * Anthracene react with maleic anhydride to yield respective Diel’s- Alder adduct uc | ooo: x — ° | Diel's-Alder adduct Anthracene Maleic anhydride 7" |QO USE OF ANTHRACENE) It is used as a wood preservative. | Used as insecticide for crops. Anthraquinone which is a precursor to dyes. -P wn e Anthracene is used as Scintillator for detectors of high energy photons, electrons and alpha particles. 5. Anthraquinone derived drugs have different actions, Emodine have purgative action, Alizarines have spasmolitic and nephrolitic action. 6. Drugs like senna, cascara and aloes contains anthraquinone asa glycone component and these drugs possess laxative /cathartic effect. {a DERIVATIVES OF ANTHRACENE| | ANTHRONE | USES: 1. It is used as a for cellulose assay 2. Itis the colorimetric estimation of carbohydrates 3. It is also used for the laxative ANTHRAQUIINONE 2-AMINOANTHRAQUINONE cr 0 Anthraquinone r 2-Aminoanthraquinone |1. INTRODUCTION 2. METHOD OF PREPARATION 3. CHEMICAL PROPERTIES 4. USE’S OF PHENANTHRENE Q) PHENANTHRENE ¢ Phenanthrene is a polycyclic aromatic hydrocarbon composed of three fused benzene rings which takes its name from the two terms ‘phenyl’ and ‘anthracene * Molecular formula:- C,H * Phenanthrene is an isomer of anthracene * Phenanthrene is a colorless, crystal-like solid but can also look yellow * The solution of Phenanthrene in benzene gives a blue fluorescence ¢ Allthe fourteen carbon atoms are sp” hybridized 9 10 \ H,S0, — \ \ > S/o UP tt 120°C Phenanthrene mae 2-phenanthrene 3-phenanthrene | sulphnic acid sulphnic acid fe = ” * Phenanthrene undergoes acylation with acetyl chloride in the presence of aluminium chloride at 0°C to yield 9-acetyl Phenanthrene H3COC O ma RY - er EE Phenanthrene 9-Acetyl phenanthrene (Q USE OF PHENANTHERENE Phenanthrene can be used in the manufacture of pesticides and dyes. 2. After conversion processing it can be used to produce dyes, drugs and resins. 3. Itis used as a stabilizer of the high efficiency and low toxicity pesticides and smoke less powder explosives. || 4. Phenanthrene quinone can be used as dyes, fungicide and polymerization inhibitors. Perhydrophenanthrene is used in production of jet fuel. Phenanthrene sulfonic acid can be used as binder and tanning. In paper industry Phenanthrene is used as pulp antifogging agent Phenanthrene is also used for synthesizing alkalosis morphine and caffeine, dimethyl morphine. ernanwUNIT issih 1. INTRODUCTION 2. USE’S OF DIPHENYL METHANE 3. METHOD OF PREPARATION 4. CHEMICAL PROPERTIES Q) DIPHENYL METHANE * Diphenyl methane is an organic compound consists of methane where in two hydrogen atoms are replaced by two phenyl groups * The diphenylmethyl group is also known as benzhydryl * IUPAC - 1,1'-Methylenedibenzene * Chemical formula - C,3H,». CH, (Q USE OF DIPHENYL METHANE * The fragrance industry uses diphenylmethane both as a fixative and in | soaps to scent them. | + This can be used in pesticides and insecticides * The plasticizer diphenylmethane can be used as a dye carrier, a solvent for dyes, or a plasticizer to improve dyeing properties.C) METHOD OF PREPARTAION 1. Friedel-Crafts condensation: When benzyl chloride is reacted with benzene in presence of AICI;, as catalyst, diphenylmethane is obtained. Onno © + O-) Benzyl Paes Benzene Diphenyl methane 2. From formaldehyde: One molecule of benzaldehyde react with two molecule of benzene in presence of conc. H,SO, to yield diphenyl methane H,SO, lr aN 2) + weHo =" >. ¢ pte _) + tho Benzene Formaldehyde Diphenyl methane 3. From Grignard reagent: Phenyl magnesium bromide react with benzyl chloride to yield diphenyl methane -709 ¢ Y-cx,c1 + CeHsMgBr 00770°C (pot aN Benzyl Phenyl chloride magnesium bromide Diphenyl methane 4. Wolf kishner: Benzophenone react with HI and red phosphorus at 160 °C under pressure by wolf kishner reduction. Wolf kishner oO fj i reduction OAD Te en _) i Benzo phenone cS Dipheny! methane() CHEMICAL REACTION Diphenyl methane react with nitrating mixture whereby first nitro group enter into the 4" and the second nitro group enters into the 4’ position Cr) BS on Ca) Diphenyl methane 4,4'-Dinitrodiphenyl methane Diphenyl methane react with bromine to yield diphenyl methyl bromide GeO Oto Diphenyl methane Diphenyl methyl bromide Dipheny] methane react with chromic acid to yield benzophenone Cr) Sem OD) Diphenyl methane BenzophenoneUNIT - IV HENYL METHANE ee Joints to be covered | 1. INTRODUCTION 2. USE’S OF TRIPHENYL METHANE 3. METHOD OF PREPARATION 4. CHEMICAL PROPERTIES Q) TRIPHENYL METHANE Triphenylmethane, is the hydrocarbon with the formula (C,H;)3;CH IUPAC - 1,1',1’-Methanetriyltribenzene Chemical formula - C,,H.¢ OHO Q) USE OF TRIPHENYL METHANE * Triphenylmethane is the basic skeleton of many synthetic dyes, many of them are pH indicators, and some display fluorescence(CQ METHOD OF PREPARTAION 1. Friedel-Crafts reaction: When 3 molecule of benzene in reacted with one molecule of chloroform in the presence of AICI,, as catalyst, triphenyl methane obtained AICI, 3 + CHCl; ——» (\- H Benzene Chloroform Oo Triphenyl methane 2. From Benzaldehyde: Benzaldehyde react with benzene in the presence of ZnCl, to yield triphenyl methane ae ea OG Org OF Benzaldehyde Benzene Triphenyl methane 3. From biphenyl: Biphenyl react with dichloro toluene to yield triphenyl methane DX XX) + Ore oF Biphenyl Toluene YY Tripheny! methane() CHEMICAL REACTION “ REACTION WITH SODIUM Triphenyl methane react with sodium or in liquid ammonia to yield triphenyl methyl sodium 0 Cpt + ve BO ao O O Tripheny! methane Triphenyl methyl sodium “* BROMINATION Triphenyl methane react with bromine to yield triphenyl methyl bromide Triphenyl methane Triphenyl methyl bromide “* OXIDATION * On oxidation of triphenyl methane yield triphenylcarbinol