P: ISSN No. 2231-0045 RNI No.  UPBIL/2012/55438 VOL.- XI , ISSUE- IV May  - 2023
E: ISSN No. 2349-9435 Periodic Research
Synthesis of 5-chloro-2,3-dihydro-1H-inden-1-One Using Green Heterogeneous Catalyst
Paper Id :  17602   Submission Date :  13/05/2023   Acceptance Date :  21/05/2023   Publication Date :  25/05/2023
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Sunil Kumar Pandey
Research Scholar
Applied Science
Dr. K.N. Modi University
Newai, Tonk, Rajasthan, India,
M. Shahid
Assistant Professor Applied Science
Dr. K.N. Modi University
Newai, Tonk, Rajasthan, India
R. N. Sharma
Principal
Chemistry
SHS Govt PG College, Dhanapur
Chandauli, Uttar Pradesh, India
Abstract Heterogeneous catalysis holds many potentials for replacing reagents in the field of green chemistry and environment protection. Yttria zirconia based heterogeneous catalysis shows the Lewis acid catalytic properties and play a vital role in the synthesis of an intermediate 5-chloro-2, 3-dihydro-1H- inden-1-one with high yield and selectivity.
Keywords Cyclisation, Heterogeneous Catalysis, Green Chemistry, Selectivity.
Introduction
The application of acid catalysts is very important in the pharmaceutical industry application chemical and refinery industries, and those technologies employing highly corrosive, hazardous and polluting conventional liquid acids and Lewis acids such as Phosphoric acid, PPA, nitric acid, H2SO4, HCl, HF, HClO4, H3PO4, AlCl3, BF3, ZnCl2 and SbF5 to overcome the above problem solid green catalyst introduced in the synthesis of pharmaceutical, chemicals and refinery industry. Heterogeneous catalyst are characterized by various advantages which include easy handling, recyclability in the process engineering, catalyst regeneration and cost effective. This phenomenon decreasing reactor and plant corrosion problems and environmentally safe disposal [1-15]. Over the past few decades, zirconia (ZrO2) based solid acids have received much attention, among other solid acids, due to their superior catalytic activity for hydrocarbon conversions at mild conditions [2,8,14-18]. 5-chloro-2,3-dihydro-1H-inden-1-one which is an intermediate raw material for medicines, such as antitussive and expectorant, and used in many purpose to synthesize these molecules using green chemistry tool. 5-chloro-2,3-dihydro-1H-inden-1-one involved in the Irie′s synthesis of substituted pyridines [19] 5-Chloro-1-indanone may being as starting reagent for the preparation of 5-chloro-2-methoxycarbonyl-1-indanone [20] .Having important biomedical compounds such as anticonvulsants, anticholinergics and diary sulfonylureas, having potential activity against solid tumors.
Aim of study This prompted us to synthesize 5-chloro-2,3-dihydro-1H-inden-1-one using green catalyst, and here we report that an yttria-zirconia based Lewis acid serves as an excellent catalyst for the selective cyclisation of 5-chloro-2,3-dihydro-1H-inden-1-one during . T Aimed to develop an application of green catalyst in synthetic organic chemistry, the Yttria-zirconia based acidic was found to be an extremely efficient catalyst for the Diels Alder 22-28 reaction and Tran’s esterification 23-28 of b- keto esters 24. However, the reaction of 5-chloro-2,3-dihydro-1H-inden-1-one with Aluminum chloride or potassium fluoride is found to be sluggish with solvent andcatalyst (Table 1, entries 2) and reaction with solvent and catalyst (20 mol %) gives better yield and selectivity of the product. (Table 1, entries 2)
Review of Literature

There are many more methods are already known in literature to prepare 5-chloro-2,3-dihydro-1H-inden-1-one.

An a method using m-chloro phenyl propionic acid through palladium carbon reduction hydrogenation with a chloro-cinnamic acid, chlorination obtains m-chloro phenyl propyl alcohol acyl chlorides, and last cyclization obtained. The drawback of these method mainly cyclization time there is selectivity issues, impurity formation like 7-chloro-2 indone can be formed, the chloro-1-indone of 3-bis-, and large quantity of excess hydrogen chloride liberated.

Although content is not very high and product impure, bring unnecessary problem at isolation stage separating-purifying.

An another method cyclization uses has aluminum chloride, boron trifluoride, trifluoromethanesulfonic acid, hydrofluoric acid, the vitriol oil or solid acid etc

One, obtain through friedel-crafts acylation 14,15 under catalyzer with 3-chlorpromazine chloride and chlorobenzene, catalyzer has aluminum chloride, boron trifluoride, trifluoromethanesulfonic acid [17-18], hydrofluoric acid etc.

The trifluoromethanesulfonic acid used in this method has strong corrodibility, can cause serious burn, easily the health of injury operator; In addition, a large amount of trifluoromethanesulfonic acids is difficult to process, the yield of 4 '-dichloropropiophenone is too low [24-30].

Our current to develop the comparatively easy of a kind of 5-of synthesis chloro-1-indone and be easy to amplify technique, substantially pollution-free, with the help of heterogeneous catalyst during cyclisation of the reaction.  

Main Text

Methodology
Procedure for the preparation of the catalyst: The catalyst prepared using a mixture of aqueous solutions of yttrium nitrate and zirconyl nitrate (molar ratio 16:84) with aqueous ammonia (28%) under vigorous stirring until a pH value of 8-8.5 was achieved and a precipitate was formed. Downloaded by: National University of Singapore. Copyrighted material. LETTER Yttria-Zirconia Based Lewis Acid 209 , Synlett 2001, No. 2, 206–209 ISSN 0936-5214 © Thieme Stuttgart · New York. Precipitate was washed with deionized water, dried at 110°C, treated with 2N sulfuric acid, dried again at 120°C for 24 h. The subsequent programmed calcination at 500°C for 3 h at a heating rate of 2°C min- 1 resulted in a highly acidic material. (a) 5-chloro-2,3-dihydro-1H-inden-1-one In a typical experimental procedure, compound 1 (20 mmol; 1.0 equiv) was added in toluene 20 ml of dry toluene and followed by addition of catalyst (10 % by weight), and the mixture was heated refluxed for 100-110 oC the indicated length of time (Table 1–2). The progress of the reaction monitored by monitored by TLC. After completion of reaction, the catalyst was filtered and kept aside for recycling purpose. Filtrate mother liquor diluted with water (30 ml). The organic layer was separated, washed with 10 % aq. NaHCO3, brine followed by water and dried over Na2SO4. The solvent was removed and the crude product was chromatographed on a silica gel column to afford the pure product using hexane ethyl acetate (9: 1). After the reaction, the catalyst is recovered with retention of its catalytic activity. It can be further reactivated for reuse by heating it at 500 °C in the presence of air. The substrates examined in our studies and the results obtained are summarized in Table 1 and table 2. Table1: Experimental detail of 5-chloro-2,3-dihydro-1H-inden-1-one from 3-chlorophenyl propionic acid using green Yttria zirconia based heterogeneous catalysis are summarized in below table.
Sampling

Product were characterized by 1H NMR CDCl3 2.47 (3H, S), 6.38-6.40 (2H, dd), 7.22-7.26(2H, dd), 9.48 OH (bs) and

IR in cm-1: ; C=O peaks 1715 cm-1, OH peak 2400 cm-1, Mass spectrum MS+1, (167) and its correspond to the authentic sample 28.

Tools Used The following tools used during experimental study
1. TLC
2. Column chromatography
3. NMR
4. Mass spectrometer
5. Infra red spectrometer
Statistics Used in the Study

The Experimental details are summarized in Table-1  & Table-2
Table1: Experimental detail of 5-chloro-2,3-dihydro-1H-inden-1-one from 3-chlorophenyl propionic acid  using green Yttria zirconia based heterogeneous catalysis are summarized in below table.

Isolated yield:*b Column chromatography *** NA: Not applicable 
Table 2. Summary of experimental detail with respect to variation of catalyst mol % / time/ temperature verses % Yield. 

Isolated yield:*b Column chromatography *** NA: Not applicable 

Analysis
Sample analyzed  and matched with Authentic samples using NMR , IR 
Result and Discussion

The literature showed highly corrosive, hazardous and polluting conventional liquid acids and Lewis acids such as Phosphoric acid, PPA, nitric acid, H2SO4, HCl, HF, HClO4, H3PO4, AlCl3, BF3, ZnCl2 to overcome the above process. We have plan to synthesize using Green catalyst. Which gives high selectivity, easy work procedure and high yield > 98 % in very short span of time.

Findings Selectivity, Easy workup procedure and Isolated yield > 98 %
Conclusion Yttria zirconia based green catalyst approach towards synthesis of 5-chloro-2,3-dihydro-1H-inden-1-one from 3-chlorophenyl propionic acid shown better catalytic properties with respect to the selectivity and easy workup procedure. These solid acid catalysts having strong incentives to which one can replace the unfriendly AlCl3/H2SO4 and HF acids in many industrial processes, and in this direction, there is a lot of scope and advantage to work. Catalytic activity of these catalysts depends on the method of preparation, precursors used, nature of promoting agents, calcination temperature etc. But still there is tremendous scope to study and exploit these catalysts for numerous reactions as a green chemistry.
Suggestions for the future Study The catalyst can be used for further study after recycling and calcination @ 500 temprature.
Acknowledgement SKP thanks for giving opportunity at Dr. K.N. Modi Newai Rajasthan for research work. We are grateful to Dr. Ram Naresh Sharma Principal, SHS Govt PG College Dhanapur, Chandauli and for his constant encouragement and support.
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