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Green Organic Reaction with

Water as A Solvent

Inderdip P. Shere

M. Chem. Eng.-1 1A V P


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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.

` 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.

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` 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.

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` 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 activecompounds and antibiotics. Also use in dyes, organicsemiconductors, DNA cleaving agents etc.

` Condensation of an aryl 1, 2-diamine with 1, 2-dicarbonyl compounds.

` Have poor yields, critical product isolation procedures,expensive and detrimental metal precursors and harshreaction conditions.

` Quinoxaline can be obtain from 1,2- diketones and 1,2-diamines using water soluble can as a catalyst. Its haseconomic and environment advantages.

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` Electron donors and acceptors in photo-initiated

polymerization of Acrylates and Methacrylates. Also

use as laser dyes

` Knoevenagel condensations and Michael additions ofaldehydes with 1,3-cyclic diketones.

` NaOH, KOH, Piperidine and Proline as catalyst which

requires organic solvents.

` Tetraketones can be developed in pure water. Furtherpurication procedure is just ltration, washing and

drying. More economical.

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Components Traditional methods Problem Green method Advantages

Thioesters Thiols with acid chloride /

acid anhydride

Corrosive

reagents

Harsh

reaction

conditions

Expensive

catalysts or

reagents

Unfriendlyorganic

solvents.

Tertiary

thioamides in

aqueous mediawith nai,

DABC,

HTABO

Single- step

Eco-friendly

Diverse

thioesters

High yields.Thiols with carboxylic

acids

Thiols with esters or N-

acylbenzotriazoles

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Alkylated

nitrogen

heterocyclic

compounds

Ring opening of epoxides

with nitrogen heterocycles

Catalysts

cannot be

recovered.

Hazardousand toxic

wastes.

Ordered

mesoporous

material were

used as a

catalyst in

water

Reuse of

catalysts

No organic

solventsHigh yields.Enantioselective addition of

indoles with aromatic

epoxides h

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-oxo ester Carbonylation of -halo

ketones

Harmful

reagents

Corrosive

and toxic

reaction

conditions

catalytic

addition in

aqueous

medium using

the water-

soluble

Ruthenium(II)

complex

Single- step

Eco-friendly

Economical

High yields.

The two-step hydration /esterication of propargylic

alcohols

Oxidation of ketones with

metalacetate complexes

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Quinoxaline

derivatives

condensation of an aryl 1,

2-diamine with 1, 2-

dicarbonyl compounds

Poor yields

Difficulties

in productisolations

Expensive

catalysts or

reagents

Harsh

reaction

conditions

Synthesis using

cheap and

readilyavailable CAN

as a catalyst

Economical

Eco-friendly

Efficientcatalytic

system

High yields.

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Tetraketones Knoevenagel condensations

and Michael additions of

aldehydes withcyclohexane-1,3-diones, or

other types of 1,3-cyclic

diketones

Alkaline

reagents

Expensivesurfactant

reagents

Unfriendly

organic

solvents.

Using pure

water as

solvent withoutcatalyst

Single- step

Eco-friendly

Roomtemperature.

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 otherbenefits.

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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 catalystswhich 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 ofsolvents, usually chlorinated solvents.

` In greener approach solvent system consist of waterand acetonitrile

` Other system is use of (DMC)water with co oxidantssuch as sodium hypochlorite potassium hydrogen

persulfate` Simpler, environmentally friendly, solvent system canbe used for wide range of substrates.

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` Pericyclic organic reactions used for polymer cross-

linking 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 sidereactions.

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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 alkalineconditions 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 Traditional

method

Problem Green approach

Reduction of

Nitroarenes

Catalytic

hydrogenation

using raney Ni,

Pd/C and PtO2.

Expensive and a

moisture-sensitive

reagent

Organic solvent,

Pressurize reactor

with hydrogen gas

Coupling of

aromatic imines by

zinc metal and

NH4Cl in water

Chemo-selective

reduction of nitro

groups using

metallic reducingreagents

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Process Traditional

method


Knoevenagel

condensation

Performed in

organic solvents

with common bases

Its is usually

performed in

organic solvents

DABCO-base

ionic liquids are

water base catalyst

Compatible with

various aldehydes

and aliphatic

ketones.

A wide range of

catalysts

immobilized on

polymers

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Process Traditional

method


Ruthenium

tetraoxide

oxidations

Performed with co-

oxidant in a

mixture of solvents

Chlorinated

solvents, (carbon

tetrachloride)

oxidations is done

in dimethyl

carbonate (DMC)water as a solvent

system

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Process Traditional

method


Ene reaction Ene reaction are

direct reaction

Higher reaction

temperatures (140-

300c)

Undesirous side

reactions

Dangerous and

expensive

polymerizationinhibitors

Water and ethanol

can be use as

solvents

Acceleration of

ene reactions

Inhibition of side

reactions.

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Process Traditional

method


Epoxidation of , -

unsaturated ketones

Using hydrogen

peroxide under

alkaline conditions

in methanol system

Large amount of

methanol

0-2 C with H2O2and 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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` Roger A. Sheldon, Green Chem., 2005, 7, 267278

` G. H. Penn and F. Liu, J. Org. Chem., 1994, 59, 2608

` Hassan Zali Boeini and Maryam Eshghi Kashan, GreenChem., 2009, 11, 19871991.

` Cadierno, Javier Francos and Jos e Gimeno, GreenChem., 2010, 12, 135143

` Takehito Tsukinoki and Hirohisa Tsuzuki, GreenChemistry, 2001, 3, 3738

` Judith Cornely, Leyda M. Su Ham, David E. Meadeaand Veljko Dragojlovic, Green Chemistry, 2003, 5, 3437

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THANK YOU.

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