Presentation for Internal Project Review Studies on Synthesis of Organic Compounds having Commercial Application by Green Chemical Methods

by Dr. B.Vijayakumar

Department of Chemistry Vel Tech High Tech Dr.Rangarajan Dr.Sakunthala Engineering College Avadi, Chennai-600 062.
22-01-2012

Description of the project: In the proposed project, novel methods are to be developed to obtain industrially derivatives, important products benzyl such as -damascone, etc. For quinoline example, arenofurans, nicotinate,

esterification of phenols with sterically hindered or long chain alcohols by conventional methods is difficult. This can be achieved in presence of eco-friendly catalysts, particularly clays, in presence of solvents or under solvent-free conditions. In the present proposal, Indian clays will be modified systematically using dilute solutions of mineral and/or organic acids, and metal salts at different temperatures and time intervals. Further, several ion exchanged and clay supported catalysts will be prepared using various reagents such as heteropoly acids, metal salts, etc. to obtain them in desired acidity.
22-01-2012

Modification of clays and their applications

Clays are layered hydrous aluminosilicates composed of tetrahedral silicate and octahedral aluminate sheets.

Acid Activated Clays (Both Lewis & Brnsted) Cation Exchanged Clays (Brnsted acid Catalysts) Surfactant Modified Clay (Adsorbents)

Natural clay
Clay supported Reagents (Redox catalysts) Pillared Clays (Lewis acid Catalysts)

Vijayakumar, B. Clay Catalysts in Organic Synthesis (Synlett Spotlight 81) Synlett 2, 2004, 388-389.
22-01-2012

22-01-2012

Simple representation of clay

22-01-2012

Smectite (2:1)

WATER MOLECULES AND CATIONS

22-01-2012

Advantages of clay catalysts

Naturally available Cheap/Economic Easy to modify Easy to handle Possess both Lewis and Brnsted acidity Acidity can be controlled Reusable Eco-friendly

22-01-2012

Objectives
1. to prepare indigenous smectite clays (acid treated, exchanged, and supported) with different acidities. 2. to make a systematic study of the relationship between properties of catalysts and their catalytic activities. 3. to explore and optimize conditions to synthesize organic compounds of commercial importance. 4.to study the catalytic activities of the samples prepared for the synthesis of valuable products such as esters, quinolines, imidazole derivatives, arenofurans, quinazolinones, damascones, etc.

22-01-2012

Preparation of cation exchanged clays

Clay

Mn+-ion solution

Stirred at RT

Mn+-exchanged clay suspension

Washed with distilled water

Mn+-exchanged clay catalyst

Dried at 100oC

Mn+-exchanged clay

22-01-2012

Preparation of acid activated clays

Clay

Mineral acid (Dil. Solution)

Stirred at 90- 95oC

Acid-clay suspension

Washed with distilled water

Acid activated clay catalyst

Dried at 100oC

Acid activated clay

22-01-2012

Preparation of supported clay catalysts

Clay

Inorganic salt in solvent

Stirred at RT

Clay-inorganic salt suspension

Solvent was removed under vacuum

Inorganic salt/clay catalyst

Dried at 100oC

Inorganic salt/clay

22-01-2012

(i) Synthesis of 4-substituted-2-(1-(phenylsulfonyl)-1H-pyrrolo[2,3b]pyridin-3-yl)quinolines:

SO2Ph

7-azaindole-3-carboxaldehyde 1 can be obtained from 7azaindole in two steps. Treatment of 1 with substituted aniline 2 in presence of clay catalysts would form an N-aryl aldimine intermediate, which subsequently undergoes
1
N

+
O

H2N

2 Catalyst Solvent
R R'

[4+2]-cycloaddition with substituted alkyne 3 followed by aerobic dehydrogenation to obtain quinoline derivatives.
22-01-2012
R' N N

4
SO2Ph

(ii) Synthesis of new heteroaryl substituted quinolines:

OH CHO R N OCH3

NC

CN

Malononitrile

1-Naphthol

Substituted 2-methoxy quinoline-3-carbaldehyde Clay catalysts

NH2 R CN N OCH3

Heteroaryl
22-01-2012

substituted

quinolines

and

their

derivatives

exhibit

pharmacological activity such as aldosterone synthase (CYP11B2) inhibitors, neurokinin (NK)-2/NK-3 receptor ligands, etc.,

(iii) Synthesis of tetrasubstituted imidazoles:

R' R N Ph Ph N

Ph

Ph

Catalyst + R'
NH2 + CH3COO NH4
+

RCHO +
O O

Functionalized imidazoles consist of an important class of pharmacologically active compounds that have a variety of interesting properties. Benzil, aldehyde, amine and ammonium acetate are reacted in presence of a catalyst to form a tetrasubstituted imidazole.

22-01-2012

(iv) Synthesis of arenofurans:

OH NO2

O R1 R2

Clay catalysts

R2

+
R

R1 R

Arenofurans are present in many natural products that show fungicidal, antimicrobial, insecticidal, antiproliferative, cytotoxic and antioxidant properties. Phenol or substituted phenol or naphthol can be reacted with nitroalkene in presence of clay catalyst to form corresponding arenofurans by a cyclization reaction.

22-01-2012

(v) Synthesis of 4(3H)-quinazolinones:

H2N H2N N R

Metal salt/Clay + R-CHO

NH

Anthranilamide
O

Quinazolinone derivatives have drawn much attention due to their broad range of pharmacological activities, such as anticancer, antiinflammatory, anticonvulsant and antidituric activities. Anthranilamide, aldehyde and a metal salt supported clay catalyst will be reacted in refluxing solvent to obtain the corresponding 4(3H)-quinazolinones.

22-01-2012

Any literature survey done? If so, please give details: There are reports on clays as catalysts in organic synthesis in the literature. An important list of references is as follows. [1] Rothenberg, G., Catalysis: Concepts and Green Applications, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2008. [2] a) McCabe, R.W., In Inorganic Materials: Clay Chemistry, Bruce, D.W. and O'Hare, D., Eds.; John Wiley and Sons: Chichester, 1992, 295-351. b) Smith, K., " Solid Support and Catalyst in Organic Synthesis" Ellis Harwood Chichester 1992. c) Augustine, R. L., "Heterogeneous Catalysis for the Synthetic Chemist" Marcel & Dekker 1996. [3] Balogh, M. and Laszlo, P., Organic Chemistry Using Clays, Springer: Berlin, 1993. [4] a) Vijayakumar, B., Clay Catalysts in Organic Synthesis, Synlett 2004,2,388. b) Nagendrappa, G., Appl. Clay Sci. 2011, 53, 106.
22-01-2012

What is the state of the art in the area in which you propose to take up the project: Most of the currently conducted industrial reactions involving

pharmaceuticals, perfumes and petrochemicals make use of metals, metal salts, metal oxides, mineral acids, metal hydroxides, microporous zeolites, ion-exchange resins, etc. Many reactions are performed under harsh conditions with toxic and expensive reagents. The organic compounds to be synthesised in the project have been prepared using expensive and toxic reagents and are valuable products. For example, industry. -damascone is an important compound in perfume

22-01-2012

Methodology to execute the project: 1. Procurement of indigenous clays and preparing acid treated, supported, and various cation-exchanged clays, 2. Characterisation of the catalyst samples by XRD, XRF, TGA, DTA, FTIRDRIFTS, TPD-NH3, and BET surface area measurements, 3. Utilisation of these clay catalysts (catalytic activity) for carrying out organic transformations, 4. Optimisation of the reaction conditions for obtaining the value added products mentioned in the project in high yields, and 5. Synthesis of the organic compounds of interest in perfumes, pharmaceuticals, biologically activity, etc. and characterising the organic compounds by IR, HRMS and NMR.

22-01-2012

9. Expected outcome of the project (Utility or application): Outcome of the project may evince some interest from industries, which are presently using conventional acid catalysts such as H2SO4 and HCl. An associated socio-economic factor would be the indirect benefit, the claymining activity would derive, which possibly might lead to the cost reduction and better utilisation of industrial resources. Further, the project has commercial application and/or patentability. The catalysts prepared in the proposed project can be reused and the organic compounds are used in perfumery, cosmetics, and pharmaceuticals. The main advantage of this method is elimination of pollutant organic solvents and the environmentally friendly character.

22-01-2012

Thank you for your kind attention

22-01-2012