Green Organic Reaction with Water as A Solvent

AV P

Inderdip P. Shere M. Chem. Eng.-1

CONTENTS
Introduction Objective Organic products
Table of comparison

Organic process
Table of comparison

Conclusion
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What is green chemistry?

green chemistry efficiently utilizes (preferably renewable) raw materials, eliminates waste and avoids the use of toxic and/or hazardous reagents and solvents in the manufacture and application of chemical products.

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What's so special about organic synthesis? What special importance does water have?

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Only concentrate over organic synthesis in water under the green chemistry. Only economical and environmental friendly with relative higher yields. Reactions having overall advantage over traditional methods. Check upon intangible parameters Ionic liquids and alcohols curtained form the study.

These are bioactive organic derivative crucial in metabolism. Usually prepared using Thiols with acid catalyst, anhydrides, carboxylic acid. It require long time, less yield (16-32%), catalyst or reagents and unfriendly organic solvents. And all the reactions starts with thiols. In a single step reaction in water using NaI, DABCO, and HTAB. We get yield upto 93%

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Indoles and Pyrroles are antibiotic and have anticancer activities are important for pharmaceutical, biological and synthetic chemical industries. Ring opening of Epoxides with nitrogen heterocycles Require highly corrosive acidic or basic catalysts and not recyclable, produces hazardous wastes. Using Mesoporous material in water gives good yield without polluting the environment.

Intermediates for -hydroxy ketones and use in biochemistry and pharmaceutical. Carbonylation of -halo ketones or two-step hydration/esterication of propargylic alcohols Reagent used are corrosive and toxic which adversely affect the environment. Catalytic addition of carboxylic acids to terminal propargylic alcohols in aqueous medium using the water-soluble Ruthenium(II) complex. It can further tolerate several functional group
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Components of several pharmacologically active compounds and antibiotics. Also use in dyes, organic semiconductors, DNA cleaving agents etc. Condensation of an aryl 1, 2-diamine with 1, 2dicarbonyl compounds. Have poor yields, critical product isolation procedures, expensive and detrimental metal precursors and harsh reaction conditions. Quinoxaline can be obtain from 1,2- diketones and 1,2diamines using water soluble can as a catalyst. Its has economic and environment advantages.

Electron donors and acceptors in photo-initiated polymerization of Acrylates and Methacrylates. Also use as laser dyes Knoevenagel condensations and Michael additions of aldehydes with 1,3-cyclic diketones. NaOH, KOH, Piperidine and Proline as catalyst which requires organic solvents. Tetraketones can be developed in pure water. Further purication procedure is just ltration, washing and drying. More economical.
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Components Thioesters

Traditional methods Thiols with acid chloride / acid anhydride Thiols with carboxylic acids Thiols with esters or Nacylbenzotriazoles

Problem Corrosive reagents Harsh reaction conditions Expensive catalysts or reagents Unfriendly organic solvents.

Green method Tertiary thioamides in aqueous media with nai, DABC, HTABO

Advantages Single- step Eco-friendly Diverse thioesters High yields.

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Components Alkylated nitrogen heterocyclic compounds

Traditional methods Ring opening of epoxides with nitrogen heterocycles

Problem

Green method Ordered mesoporous material were used as a catalyst in water

Advantages Reuse of catalysts No organic solvents High yields.

Catalysts cannot be recovered. Hazardous Enantioselective addition of and toxic indoles with aromatic wastes. epoxides h

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Components -oxo ester

Traditional methods Carbonylation of -halo ketones The two-step hydration / esterication of propargylic alcohols Oxidation of ketones with metalacetate complexes

Problem Harmful reagents Corrosive and toxic reaction conditions

Green method catalytic addition in aqueous medium using the watersoluble Ruthenium(II) complex

Advantages Single- step Eco-friendly Economical High yields.

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Components Quinoxaline derivatives

Traditional methods condensation of an aryl 1, 2-diamine with 1, 2dicarbonyl compounds

Problem Poor yields Difficulties in product isolations Expensive catalysts or reagents Harsh reaction conditions

Green method Synthesis using cheap and readily available CAN as a catalyst

Advantages Economical Eco-friendly Efficient catalytic system High yields.

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Components Tetraketones

Traditional methods Knoevenagel condensations and Michael additions of aldehydes with cyclohexane-1,3-diones, or other types of 1,3-cyclic diketones

Problem Alkaline reagents Expensive surfactant reagents Unfriendly organic solvents.

Green method Using pure water as solvent without catalyst

Advantages Single- step Eco-friendly Room temperature. High yields.

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It gives aromatic amine use for dyes, medicines and agricultural chemicals. Catalytic hydrogenation using Raney Ni, Pd and metallic reducing reagents such as Sm, In and B10H14. It requires expensive and a moisture-sensitive reagent and an organic solvent Reductive coupling of aromatic imines by zinc metal and NH4Cl in water gives green approach and other benefits.

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Carboncarbon bond formation. Nucleophilic addition of an active hydrogen compound to a carbonyl group followed by a dehydration reaction. It generally yield alpha, beta conjugated enone. Performed in organic solvents in the presence of common bases such as ammonia, primary or secondary amines and their salts DABCO-base ionic liquids are used as a catalysts which is used in water. Provides excellent yields with 100% selectivity. Further it can be reuse.
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Oxidation of organic compounds such as, alcohols, aldehydes, alkenes, aromatic using ruthenium. Ruthenium tetraoxide used is suspension in mixture of solvents, usually chlorinated solvents. In greener approach solvent system consist of water and acetonitrile Other system is use of (DMC)water with co oxidants such as sodium hypochlorite potassium hydrogen persulfate Simpler, environmentally friendly, solvent system can be used for wide range of substrates.
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Pericyclic organic reactions used for polymer crosslinking and paper chemical synthesis, for its C-C bond forming. It requires higher reaction temperatures (140-300C) leading to side reactions. For which expensive catalysts, and harmful chlorinated solvents are used. Water and ethanol solvents have been used which accelerats the Ene reactions and the inhibition of side reactions.

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Epoxides products of , -ketones used in perfume formulations and flavoring substances. Also use for nucleophilic ring opening of the oxirane ring. Carried out using hydrogen peroxide under alkaline conditions in methanol and requires large quantities of methanol Epoxidation can be done in water at 0-2 C with H2O2 or CTAOH and using NaOH gives excellent yeids.

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Process Reduction of Nitroarenes

Traditional Problem method Catalytic Expensive and a hydrogenation moisture-sensitive using raney Ni, reagent Pd/C and PtO2. Organic solvent, Pressurize reactor Chemo-selective reduction of nitro with hydrogen gas groups metallic reagents using reducing

Green approach

Coupling of aromatic imines by zinc metal and NH4Cl in water

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Process Knoevenagel condensation

Traditional method Performed in organic solvents with common bases A wide range of catalysts immobilized on polymers

Problem Its is usually performed in organic solvents

Green approach

DABCO-base ionic liquids are water base catalyst Compatible with various aldehydes and aliphatic ketones.

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Process Ruthenium tetraoxide oxidations

Traditional method

Problem

Green approach

Performed with co- Chlorinated oxidant in a solvents, (carbon mixture of solvents tetrachloride)

oxidations is done in dimethyl carbonate (DMC) water as a solvent system

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Process Ene reaction

Traditional method Ene reaction are direct reaction

Problem Higher reaction temperatures (140300c) Undesirous side reactions Dangerous and expensive polymerization inhibitors

Green approach

Water and ethanol can be use as solvents Acceleration of ene reactions Inhibition of side reactions.

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Process

Traditional Problem method Epoxidation of , - Using hydrogen Large amount of unsaturated ketones peroxide under methanol alkaline conditions in methanol system

Green approach

0-2 C with H2O2 and using NaOH as base in water. Excellent yields.

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Water, as a solvent posses a large amount of advantages. Although, most of the organic synthesis used to be carried in conventional solvents Green chemical process in solution involves the choice of a safe, non-toxic and cheap solvent. Water is the obvious choice

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THANK YOU..
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