GREEN CHEMISTRY

Dr. Muhammad Irshad

 Green • Dimethyl Carbonates
(DMC)
Reagent

Green • Ionic Liquids (ILs)

Reagent
2
GREEN REAGENT
 Green reagent is one that reduces or eliminates the use or

generation of hazardous substances in the design, manufacture

and application of chemical products.

 Chemical developments also bring new environmental problems

and harmful unexpected side effects, as a result there is a need

for ‘greener’ chemical products.

 Green reagents have minimal side effects , and low pollutability.

3
DIMETHYL CARBONATE (DMC)
 Dimethyl carbonate (DMC) is an organic compound with the formula of

OC(OCH3)2 .

  It is a colourless, flammable liquid. It is classified as a Carbonate ester.

 It is a nonpolar aprotic solvent with good miscibility with water,

biodegrades readily in the atmosphere, and is non-toxic. 

4
DIMETHYL CARBONATE AS A GREEN
REAGENT
 Methylation and alkoxycarbonylation using DMS, CH3I, and COCl2

 Methylation and methoxycarbonylation using DMC

5
DIMETHYL CARBONATE AS A GREEN
REAGENT
 Among the specific advantages of DMC, and of alkyl carbonates in
general, is that their building block is CO2, an environmentally
benign compound, which does not cause emissions of volatile
organic compounds (VOC) in the atmosphere.
 Under both continuous flow and batch conditions, DMC can react
with a number of nucleophilic substrates such as phenols, primary
amines, sulfones, thiols, and methylene-active derivatives of aryl
and aroxy-acetic acids.

6
PROPERTIES OF DMC
 DMC is a nontoxic compound: it has not been produced from phosgene, but
by catalytic oxidative carbonylation of methanol with oxygen through a
process developed by Enichem (Italy) and UBE Industries (Japan).
 In addition to improving procedural safety, this method of producing DMC
avoids contamination from phosgene, and eliminates the need to dispose of
by-product inorganic salts.

7
PROPERTIES OF DMC
 An industrial procedure recently developed by Jiangsu Winpool Industrial
Co., China is the cleavage of cyclic carbonates .

8
PROPERTIES OF DMC

9
PROPERTIES OF DMC
 DMC is classified as a flammable liquid, smells like methanol, and does not
have irritating or mutagenic effects, either by contact or inhalation.
Therefore, it can be handled safely without the special precautions required
for the poisonous and mutagenic methyl halides and DMS, and extremely
toxic phosgene.
 DMC exhibits a versatile and tuneable chemical reactivity that depends on
the experimental conditions. In the presence of a nucleophile (Y 2), DMC
can react either as a methoxycarbonylating or as a methylating agent.

10
PROPERTIES OF DMC

Hard Nu-

Soft Nu-

11
REACTION CONDITIONS
 Reaction conditions apparently are not green: the methylating ability of
DMC can be exploited at a temperature >160º C.
 An autogenic pressure upto 3 bar required for batchwise synthesis.
 Discontinuous (batch) processes are carried out in pressure vessels
(autoclaves) where DMC is maintained as liquid by autogenous pressure.
 Instead, Continuous Flow reactions at atmospheric pressure require that
both DMC and the reagent(s) in the vapor phase come into contact with a
catalytic bed.
 DMC is used as a methylating reagent for a variety of substrates: phenols,
thiols, thiophenols, aromatic amines, arylace-tonitriles, arylacetoesters,
aroxyacetonitriles, aroxyacetoesters, alkylarylsulfones, benzylarylsulfones,
12
and lactones, either under CF or in batch conditions.
PROPERTIES OF DMC
 Methoxylation

 Methoxycarbonylation

13
CONCLUSION
 Dimethyl carbonate, as a `green' solvent and reagent, incorporates several
fundamental aspects of Green chemistry.
 Reacts selectively with a great variety of compounds as a methylating or
carboxymethylating reagent, it requires only catalytic amount of a base and
produces no waste (high atom economy).
 Several industrial procedures already use DMC as a reagent (or a solvent)
and many others are under investigation.

14
IONIC LIQUIDS
 There are four principal strategies to avoid conventional organic solvents
1. No Solvent (petrochemical industry-Greenest in chemical sector)
2. Water (Ideal )
3. Supercritical Fluids
4. Ionic Liquids (low vapor pressures at room temperature)

 Can be defined as “A liquid comprised entirely of ions”.

 An IL could contain a very large number of different ions.
 Molten salts are also IL’s but solution of salt in water will be consider ionic
solutions.
 These have high-temperature, corrosive, viscous media.
 Extremely low vapour pressure.
 Non-Flammable
 Electrically conductive and thermally stable.
15
WHY IONIC LIQUIDS ARE CALLED AS DESIGNER
SOLVENTS

 Ionic liquids are made solely of cations and anions, and

the properties of ionic liquids can be altered with the
variation in ionic component. This means their
properties can be adjusted according to the requirement
of a particular process. Hence, ionic liquids are re-
ferred as Designer solvents.

16
COMPARISON OF ORGANIC SOLVENTS WITH IONIC
LIQUIDS

17

Plechkova, N. V.; Seddon K. R. Chem. Soc. Rev. 2008, 37, 123–150

IONIC LIQUIDS IN ORGANIC
SYNTHESIS
 Catalytic  Friedel–Crafts
 Hydrogenetions  Alkoxycarbonylation
 Hydroformylations  Olefin dimerization
 Heck reactions  Diels-Alder
 Suzuki coupling  Oxidations
 Stille Coupling

18
IONIC LIQUIDS IN ORGANIC SYNTHESIS

 Diels-Alder Reaction:

19
IONIC LIQUIDS IN ORGANIC SYNTHESIS

 Heck Reaction:

20
IONIC LIQUIDS IN ORGANIC SYNTHESIS

 Wittig Reaction:

21
IONIC LIQUIDS IN ORGANIC SYNTHESIS
 Suzuki-Miyaura coupling Reaction:

22
IONIC LIQUIDS IN ORGANIC SYNTHESIS
 Stille Reaction:

23
IONIC LIQUIDS IN ORGANIC SYNTHESIS
 Friedel-Crafts Reaction:

24
IONIC LIQUIDS IN ORGANIC SYNTHESIS
 Hydrogenation Reaction:

25
IONIC LIQUIDS IN ORGANIC SYNTHESIS
 Fluorination Reaction:

26
APPLICATIONS OF IONIC LIQUIDS

Chemical industry:
 The first major industrial IL’s application was the BASIL (Biphasic Acid
Scavenging utilizing Ionic Liquids) process by BASF, in which 1-
alkylimidazole scavenged the acid from an existing process. This then results in
the formation of an IL which can easily be removed from the reaction mixture.
This increased the space/time yield of the reaction by a factor of 80,000.
 Eastman operated an IL-based plant for the synthesis of 2,5-dihydrofuran from
1996 to 2004.
 The dimersol process is a traditional way to dimerize short chain alkenes into
branched alkenes of higher molecular weight.
 Ionikylation is an IL–based process developed by Petrochina for the alkylation
of four-carbon olefins with isobutane. Their 65,000 tonne per year plant is
27
claimed to be the biggest industrial application of ionic liquids to date.
APPLICATIONS OF IONIC LIQUIDS

Algae processing:
 Algae are perhaps the most widespread organisms on Earth, occupying most
niches on the planet.
 Algae perform photosynthesis and produce high-energy molecules such as
lipids and sugars, that can be converted to useful chemicals such as
biodiesel, ethanol and other biofuels.
 To accomplish this, however, algae must be harvested and their constituents
extracted from within the cells in an economically viable industrial process.
 ILs have been shown to be effective at destroying the cell wall and releasing
cell contents using a fraction of the energy, and potentially the cost, of
current harvesting and extraction processes.
28
APPLICATIONS OF IONIC LIQUIDS
Dispersants:
 ILs can act as dispersing agents in paints to enhance finish, appearance and drying
properties. ILs are used for dispersing nanomaterials at IOLITEC (company)

Gas handling:
 The company Air Products uses ILs instead of pressurized cylinders as a transport
medium for reactive gases such as trifluoroborane, phosphine and arsine. The
gases are dissolved in the liquids at or below atmospheric pressure and are easily
withdrawn from the containers by applying a vacuum.

 IL 1-butyl-3-methylimidazolium chloride has been used for separating hydrogen

from ammonia borane.

 ILs and amines can be used to capture carbon dioxide CO2 and purify natural gas

29
 APPLICATIONS OF IONIC LIQUIDS

Nuclear fuel reprocessing:

 IL 1-butyl-3-methylimidazolium chloride has been investigated as a non-aqueous
electrolyte media for the recovery of uranium and other metals from spent nuclear
fuel and other sources.
 Protonated betaine bis(trifluoromethanesulfonyl) imide has been investigated as a
solvent for uranium oxides.
 Ionic liquids, N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and
N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide, have been
investigated for the electrodeposition of Europium and Uranium metals respectively.

30
 APPLICATIONS OF IONIC LIQUIDS

Solar thermal energy:

 ILs have potential as a heat transfer and storage medium in solar thermal energy systems.

 Concentrating solar thermal facilities such as parabolic troughs and solar power towers
focus the sun's energy onto a receiver which can generate temperatures of around 600 °C
(1,112 °F). This heat can then generate electricity in a steam or other cycle.

Food and bioproducts:

 IL 1-butyl-3-methylimidazolium chloride completely dissolves freeze dried banana pulp
and with an additional 15% DMSO, lends itself to Carbon-13 NMR analysis. In this way
the entire banana complex of starch, sucrose, glucose, and fructose can be monitored as a
function of banana ripening.
 ILs can extract specific compounds from plants for pharmaceutical, nutritional and
cosmetic applications, such as the antimalarial drug artemisinin from the plant Artemisia
31
annua.
 APPLICATIONS OF IONIC LIQUIDS
Waste Recycling:
 ILs can aid the recycling of synthetic goods, plastics and metals.

 They offer the specificity required to separate similar compounds from each other,
such as separating polymers in plastic waste streams. This has been achieved using
lower temperature extraction processes than current approaches and could help avoid
incinerating plastics or dumping them in landfill.

Batteries:
 Researchers have identified ILs that can replace water as the electrolyte in metal-air
batteries. Ils have great appeal because they evaporate at much lower rates than water,
increasing battery life by drying slower. Further, ILs have an electrochemical window
of up to six volts (versus 1.23 for water) supporting more energy-dense metals. 32
CLASSES OF IONIC LIQUIDS

33
EXAMPLES OF COMMON IONIC
LIQUIDS:

 Ethyl-3-methylimidazolium (EMIM) Chloride,

 EMIM dicyanamide,

 1-butyl-3,5-dimethylpyridinium bromide,

 1-Butyl-3-methylimidazolium hexafluorophosphate
[BMIM][PF6]

34
35