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Synthetic Reagents & Applications See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/325069368 ADVANCED ORGANIC CHEMISTRY-I (MPC 102T) UNIT-III: Synthetic Reagents & Applications Presentation · May 2018 DOI: 10.13140/RG.2.2.17758.95040 CITATIONS READS 0 9,194 1 author: Dr Sumanta Mondal GITAM (Deemed to be University) 208 PUBLICATIONS 336 CITATIONS SEE PROFILE Some of the authors of this publication are also working on these related projects: Methods Development and Validation of Pharmaceutical Dosage Forms View project Lecture Notes View project All content following this page was uploaded by Dr Sumanta Mondal on 20 November 2018. The user has requested enhancement of the downloaded file. ADVANCED ORGANIC CHEMISTRY – I (MPC 102T) UNIT- III: Synthetic Reagents & Applications Aluminium isopropoxide - It is the chemical compound usually described with the formula Al(O-i-Pr)3, where i-Pr is the isopropyl group [–CH(CH3)2]. Description: IUPAC name: Aluminium Isopropoxide Other names: Triisopropoxyaluminium; Aluminium isopropanolate; Aluminium sec-propanolate; Aluminium triisopropoxide Chemical formula: C9H21AlO3 Molar mass: 204.25 g/mol Appearance: white solid; Melting point: 138–1420C; Density: 1.035 g/cm3(solid) Decomposes in water Solubility Insoluble in isopropanol Soluble in benzene Preparation: - This compound is commercially available. Industrially, it is prepared by the reaction between isopropyl alcohol and aluminium metal, or aluminium trichloride: 2Al + 6iPrOH → 2Al(O-i-Pr)3 + 3H2 AlCl3 + 3iPrOH → Al(O-i-Pr)3 + 3HCl Applications: 1. Meerwein-Ponndorf-Verley Reduction: In a MPV reduction, ketones and aldehydes are reduced to alcohols concomitant with the formation of acetone. 2. Reductions with Chiral Aluminum Alkoxides: The reduction of cyclohexyl methyl ketone with catalytic amounts of Aluminium Isopropoxide and excess chiral alcohol gives (S)-1-cyclohexylethanol Lecturer Notes_Dr. Sumanta Mondal_M. Pharm (Pharmaceutical Chemistry) _GITAM University Page | 1 E-mail: [email protected]; [email protected] ADVANCED ORGANIC CHEMISTRY – I (MPC 102T) UNIT- III: Synthetic Reagents & Applications 3. Diastereoselective Reductions of Chiral Acetals: Reduction of 4-t-butylcyclohexanone with aluminum isopropoxide in dichloromethane. 4. Oppenauer Oxidation: Cholestenone is prepared by oxidation of cholesterol in toluene solution with aluminum isopropoxide as catalyst and cyclohexanone as hydrogen acceptor 5. Hydrolysis of Oximes: Oximes can be converted into parent carbonyl compounds by aluminum isopropoxide followed by acid hydrolysis. Yields are generally high in the case of ketones, but are lower for regeneration of aldehydes. 6. Regio- and Chemoselective Ring Opening of Epoxides: Functionalized epoxides are regioselectively opened using trimethylsilyl azide/aluminum isopropoxide, giving 2-trimethylsiloxy azides by attack on the less substituted carbon. 7. Preparation of Ethers. Ethers (R-O-R) are prepared from aluminum alkoxides, Al(OR)3, and alkyl halides, R-X. Lecturer Notes_Dr. Sumanta Mondal_M. Pharm (Pharmaceutical Chemistry) _GITAM University Page | 2 E-mail: [email protected]; [email protected] ADVANCED ORGANIC CHEMISTRY – I (MPC 102T) UNIT- III: Synthetic Reagents & Applications Diazomethane - Diazomethane is the chemical compound CH2N2, discovered by German chemist Sir. Hans von Pechmann in 1894. - Diazomethane is a yellow, poisonous, potentially explosive compound, which is a gas at room temperature. The structure of diazomethane is explained using three resonance forms. Description: R-N=N=N (azide), Related functional groups compounds R-N=N-R (azo) IUPAC name: Diazomethane Other names: Azimethylene, Azomethylene, Diazirine Chemical formula: CH2N2 Molar mass: 42.04 g/mol Appearance: Yellow gas Odor: musty Density: 1.4 (air=1) Boiling point: - 230 C (−90 F; 250 K) Solubility: hydrolysis in water Molecular shape: linear C=N=N Dipole moment: polar Preparation of Diazomethane - Diazomethane is prepared by hydrolysis of an ethereal solution of an N methyl nitrosamide with aqueous base. Lecturer Notes_Dr. Sumanta Mondal_M. Pharm (Pharmaceutical Chemistry) _GITAM University Page | 3 E-mail: [email protected]; [email protected] ADVANCED ORGANIC CHEMISTRY – I (MPC 102T) UNIT- III: Synthetic Reagents & Applications Diazomethane has two common uses. 1. Conversion of carboxylic acids to methyl esters 2. Conversion of alkenes to cyclopropanes Lecturer Notes_Dr. Sumanta Mondal_M. Pharm (Pharmaceutical Chemistry) _GITAM University Page | 4 E-mail: [email protected]; [email protected] ADVANCED ORGANIC CHEMISTRY – I (MPC 102T) UNIT- III: Synthetic Reagents & Applications Osmium tetroxide - Osmium tetroxide [also osmium (VIII) oxide] is the chemical compound with the formula OsO4. Description: IUPAC name: Osmium tetraoxide Other names: Tetraoxoosmium; Osmium(VIII) oxide Chemical formula: OsO4 Molar mass: 254.23 g/mol 0 3 Appearance: white volatile solid; Melting point: 40.25 C; Density: 4.9 g/cm 0 0 5.70 g/100 mL (10 C) and 6.23 g/100 mL (25 C) in water Solubility 375 g/100 mL (CCl4) soluble in most organic solvents, ammonium hydroxide, phosphorus oxychloride Preparation of Osmium tetroxide: - OsO4 is formed slowly when osmium powder reacts with O2 at ambient temperature. Reaction of bulk solid requires heating to 4000 C. Applications of Osmium tetroxide: 1. Hydroxylation of Alkenes - Alkenes add to OsO4 to give diolate species that hydrolyze to cis-diols. The net process is called dihydroxylation. 2. Coordination chemistry - OsO4 is a Lewis acid and a mild oxidant. It reacts with alkaline aqueous solution to give the perosmate anion 2− 4− OsO4(OH)2 . This species is easily reduced to osmate anion, OsO2(OH)4 . - With tert-BuNH2, the imido derivative is produced: OsO4 + Me3CNH2 → OsO3(NCMe3) + H2O - Similarly, with NH3 one obtains the nitrido complex: OsO4 + NH3 + KOH → K[Os(N)O3] + 2H2O 3. Biological staining - OsO4 is a widely used staining agent used in transmission electron microscopy (TEM) to provide contrast to the image. 4. Polymer staining 5. Osmium ore refining Lecturer Notes_Dr. Sumanta Mondal_M. Pharm (Pharmaceutical Chemistry) _GITAM University Page | 5 E-mail: [email protected]; [email protected] ADVANCED ORGANIC CHEMISTRY – I (MPC 102T) UNIT- III: Synthetic Reagents & Applications Triphenylphosphine - Triphenylphosphine is a common organophosphorus compound with the formula [P(C6H5)3] often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. Description: IUPAC name: Triphenylphosphane Chemical formula: C18H15P; Molar mass: 262.29 g/mol Appearance: white solid; Melting point: 800C; Density: 1.1 g/cm3 Solubility: Insoluble in water; Soluble in organic solvent Dipole moment: 1.4 - 1.44 D; Molecular shape: Pyramidal Preparation of Triphenylphosphine: - Triphenylphosphine is a relatively inexpensive substance. It can be prepared in the laboratory by treatment of phosphorus trichloride with phenylmagnesium bromide or phenyllithium. - The industrial synthesis involves the reaction between phosphorus trichloride, chlorobenzene, and sodium. PCl3 + 3PhCl + 6Na → PPh3 + 6NaCl Applications of Osmium tetroxide: 1. Reagent in Mitsunobu reactions: In this reaction, a mixture of PPh3 and diisopropyl azodicarboxylate ("DIAD", or its diethyl analogue, DEAD) converts an alcohol and a carboxylic acid to an ester. The DIAD is reduced as it serves as the hydrogen acceptor, and the PPh3 is oxidized to OPPh3. 2. Reagent in Appel reactions: In this reaction, PPh3 and CX4 (X = Cl, Br) are used to convert alcohols to alkyl halides, forming OPPh3 as a byproduct. PPh3 + CBr4 + RCH2OH → OPPh3 + RCH2Br + HCBr3 3. Reagent in Staudinger reactions: The Staudinger reaction is a chemical reaction of an azide with a phosphine or phosphite produces an iminophosphorane. R3P + R'N3 → R3P=NR' + N2 Lecturer Notes_Dr. Sumanta Mondal_M. Pharm (Pharmaceutical Chemistry) _GITAM University Page | 6 E-mail: [email protected]; [email protected] ADVANCED ORGANIC CHEMISTRY – I (MPC 102T) UNIT- III: Synthetic Reagents & Applications N-Bromosuccinimide - N-Bromosuccinimide (NBS) is a chemical reagent used in radical substitution and electrophilic addition reactions in organic chemistry. NBS can be a convenient source of the bromine radical (Br•). Description: IUPAC name: 1-Bromo-2,5-pyrrolidinedione; Other names: N-bromosuccinimide (NBS) Chemical formula: C4H4BrNO2; Molar mass: 177.99 g/mol 0 3 Appearance: white solid; Melting point: 175 to 178 C; Density: 2.098 g/cm 0 Solubility: 14.7 g/L (25 C) in water; insoluble in CCl4 Preparation of N-Bromosuccinimide: NBS is commercially available. It can also be synthesized in the laboratory. To do so, sodium hydroxide and bromine are added to an ice water solution of succinimide. The NBS product precipitates and can be collected by filtration. Applications of N-Bromosuccinimide: 1. Addition to alkenes: NBS will react with alkenes in aqueous solvents to give bromohydrins 2. Allylic and benzylic bromination: Standard conditions for using NBS in allylic and/or benzylic bromination involves refluxing a solution of NBS in anhydrous CCl4 with a radical initiator—usually azobisisobutyronitrile (AIBN) or benzoyl peroxide, irradiation, or both to effect radical initiation. The allylic and benzylic radical intermediates formed during this reaction are more stable than other carbon radicals and the major products are allylic and
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