Title of invention: Microwave induced synthesis of Benzoyl propionic acid and their derivatives Field of invention:
It is in field of science innovation and Green technology; in which conventional method is replaced by green method i.e. microwave induced organic synthesis (MIOS) of β- benzoyl propionic acid. Microwave Technology has been used in chemistry since the late 1970s, however it has just been implemented in organic synthesis since the mid of 1980s. Microwave irradiations are a form of electromagnetic radiation that falls at bring lower frequency end of electromagnetic spectrum and lie in the 300-300000 MHz frequency range. Within this region, only molecular rotation is affected that means the molecules are align, not the molecular structure, Micro wave irradiation consists of electrical and magnetic field of which electrical field transfer energy to heat a substance. The magnetic field interaction does not normally compared to the typical energy required to cleave a bond 80-120kcal/mol. Microwave induced organic synthesis (MIOS) has attracted a considerable amount of attention in the recent years by not only reducing chemical reaction times from hours to minutes moreover reducing side reactions, increasing yields and enhances reproducibility.
Background and introduction of invention:
Microwave is a new source of energy, the energy required to bring about chemical reaction is supplied largely by external sources of heat, such as steam, hot oil, and electrical heating components. There is currently growing interest in alternative source of energy that can target specific molecules or bonds, giving both energy saving and improved selectivity. One of the new source of energy is the Bunsen burner of the 21st century i.e. microwave irradiation.
In the conventional method to prepare P-benzoyl propionic acid, we had to employ a lot of energy, time & a complicated system arrangement. Also after all this, the yield we got was not enough. To overcome all these problems, we have designed the greener way to prepare our desired product P-benzoyl propionic acid. Instead of using high energy utilizing burner, we employed the microwave oven to perform the synthesis. It brings up a huge reduction in the rate determining step. The time is reduced to 1 min to 5 min. It is time consuming and laborious process to prepare products and their work up required huge time. Microwave irradiation is new tool for green chemistry to find simplest productivity and their atomicity. β -benzoyl propionic acid has been prepared from Succinic anhydride, benzene ring containing compounds and catalyst Aluminum Chloride. Here, for the Preparation of P-benzoyl propionic acid & the derivatives, we have conducted the experiments with 3 different moieties as shown in table. They all give their respective propionic acid derivatives.
We had treated the benzene ring with the succinic anhydride along with the use of A1C13 as catalyst. A1C13 acts as highly reactive hydrogen abstracter. Whole the reaction had taken place in the influence of high energy microwave region rather than using burner. The heating with burner brought the distribution of heat energy into heating of reacting mixture containing vessel as well as the reaction mixture, whereas the microwave provides all the energy to the reaction mixture without wasting it in the unwanted things like heating of vessel. Due to the investment of whole energy for the conversion of the moiety into product, the time required for it is eventually reduce by a very large number.
Object of invention:
The present day industrialization has led to immense environmental deterioration with increasing environmental concerns and the regulatory constraints faced by the chemical and pharmaceutical industries, development of environmentally benign organic reactions has become a crucial and demanding research area in modern organic chemical research.
In this context, the present work aims for the synthesis of and their derivatives in green methods by using microwave irradiation hence the drive towards green chemistry.

The use of microwave irradiation may outperform conventional reaction conditions in several aspects, such as synthesis, easier workup, reduction of usual thermal degradation products and reduction of toxic and explosive quantities of solvents (green solvent), etc.
We had treated the benzene ring with the succinic anhydride along with the use of A1C13 as catalyst. A1C13 acts as highly reactive hydrogen abstracter. Whole the reaction had taken place in the influence of high energy microwave region rather than using burner.
The heating with burner brought the distribution of heat energy into heating of reacting mixture containing vessel as well as the reaction mixture, whereas the microwave provides all the energy to the reaction mixture without wasting it in the unwanted things like heating of vessel.
Due to the investment of whole energy for the conversion of the moiety into product, the time required for it is eventually reduce by a very large number.
Summary of invention:
The P-benzoyl propionic acid is a key precursor of 1-phenyl naphthalene and their derivatives, therapeutic medicinal drugs. Theβ -BPA is prepared by green methods i.e microwave induced organic synthesis (MIOS).
The synthesis of P-benzoyl propionic acid as take 500cc three -necked round bottom flask placed 5 g (1.28 mole) of succinic anhydride and 4.5 cc (1 mole) dry, thiophene free benzene with continuous stirring is started and 6.67 g (1.71 mole ) of powdered, anhydrous alumnium chloride (It acts as highly reactive hydrogen abstracter) is added all at once. Hydrogen chloride gas is evolved and the mixture becomes hot. It is in presence of microwave irradiation. The optimization of minimum quantity of reactant, catalyst, time and yield of products. The flask is then surrounding by cold water and 300 cc of water is slowly added from a dropping funnel insetted in the top of condensers the excess of benzene is discarded and obtained mass separates as a colourless oil which soon solidifies after cooling to 0°C, it is collected, washed with a cold mixture of 2.5 cc of concentrated hydrochloric acid and 7.5 cc of water. The crude β -BPA is dissolved in a solution of 3.75 gm of anhydrous sodium carbonate in 25 cc of water by boiling for fifteen minutes. The clear colourless filtered is transferred to 500 cc of beaker and carefully acidified with 6.5 cc of concentrated hydrochloric acid in freeze condition to maintain temperature 0-5 C by ice-salt bath. The solution is filtered by suction pump, washed with hot water, dry give β -benzoyl propionic acid. Repeat finally those compounds are characterized by IR, NMR and mass spectra.
The confirmation of above reaction optimization with minimum reactant concentration with catalyst aluminum chloride to formed effective yield. The derivatives of bbpa are confirmed by toluene and naphthalene, toluene and naphthalene on treatment with succinic anhydride form respective product. Follow the same procedure and gives desired product.
Detailed description of invention: Materials:
Succinic anhydride, aluminum chloride (A1C13), benzene, naphthalene, toluene, anhydrous sodium carbonate, concentrated hydrochloric acid, sodium chloride, Microwave (RAGA's scientific Microwave oven ).
Methods: Microwave induced organic synthesis via Friedel craft acylation reaction
Microwave induced organic Synthesis of p-Benzoyl propionic acid:
In 500cc three -necked round bottom flask placed 5 g (1.28 mole) of succinic anhydride and 4.5 cc (1 mole) dry, thiophene free benzene with continuous stirring is started and 6.67 g (1.71 mole ) of powdered, anhydrous alumnium chloride (It acts as highly reactive hydrogen abstracter) is added all at once. Hydrogen chloride gas is evolved and the mixture becomes hot. It is in presence of microwave irradiation, optimization of minimum quantity of reactant, catalyst as well as time and yield of products. The flask is then surrounding by cofd water and 300 cc of water is sfowfy added from a dropping funnei inserted

in the top of condensers the excess of benzene is discarded and obtained mass separates as a colorless oil which soon solidifies after cooling to 0°C, it is collected, washed with a cold mixture of 2.5 cc of concentrated hydrochloric acid and 7.5 cc of water. The crude p -BPA is dissolved in a solution of 3.75 gm of anhydrous sodium carbonate in 25 cc of water by boiling for fifteen minutes. The clear colourless filtered is transferred to 500 cc of beaker and carefully acidified with 6.5 cc of concentrated hydrochloric acid in freeze condition to maintain temperature 0-5°C by ice-salt bath. The solution is filtered by suction pump, washed with hot water, dry give β-benzoyl propionic acid. Reapet finally those compounds are charcwrized by IR, NMR and mass spectra.
Derivatives of p-benzoyl propionic acid
1. p-Toluenyl propionic acid (2):
Treat the Toluene with the Succinic anhydride along with the AlCl3 The mixture was taken into microwave oven & the microwaves are irradiated on it. This yields 2- Methyl β-benzoyl propionic acid. The time calculated for this process is 1.34 minutes.
2. p-Naphthoyl propionic acid (3):
Treat the Naphthalene with the Succinic anhydride along with the A1C13. The mixture was taken into microwave oven & the microwaves were irradiated on it. This yields 2- Naphthoyl propionic acid.

1.Benzene:

2. Toluene:

Mechanism of Synthesis of β-Benzoyl propionic acid:
Results and Discussion:
1. Infra red spectrum:
a) β-benzoyl propionic acid

2. H'NMR spectrum:
a) p-benzoyl propionic acid

Table No.l: Characterizations of synthesis of β benzoyl propionic acid and their derivatives

s.
N. Reactant Product Molecular formula Time (min.) Yield(%) Melting Point
(0°C) Infra Red (IR)
(cm1) H'NMR
(ppm) Mass
(gm)

Conv MW Conv MW

1 Benzene β-benzoyl propionic acid(l) C10H10O3 45 3.23 80.40 90.30 118 1242, 1677, 2665, 2763, 2919 2.5(2H)t, 3.2(2H)t, 7.5(3H)d, 7.9(2H)d, 12.14(lH)s 175.6, 178.2, 215
2 Toluene β-Toluenyl propionic acid (2) CnH1203 38 1.34 78.50 87.34 104 1222,168 2.99, 2658.01, 2921.31, 2.3(3H)s,
2.5(2H)t,
3.23(2H)t,
7.3-
7.8(5H)m,
12.2(lH)s 175,192 ,218.
3 Naphthal ene β-Naphthoyl propionic acid (3) C14H12O3 60 0.17 74.32 86.23 96 1169.29, 1674.97, 2919.26, 3046.20 2.5(2H)t,
3.4(2H)t,
7.3-
8.6(7H)m,
12.04(lH)s 220,228 ,251.

Conclusion:
In present study is seen that synthesis of β benzoyl propionic acid via friedel craft reaction using aluminum trichloride of thermal heating is successfully replaced by microwave irradiation. In comparative study of friedel reaction with conventional (thermal heating) to Green method (Microwave irradiation) is better with respect to time, yield. So, it is a new tool for synthesis of β benzoyl propionic acid and their derivatives.
References:
1. Fraunhofer-GeseJJschafl (New Jersey Institute of Technology), Microwave-assisted synthesis of perfluorophthalocyanine molecules, WO 2009139973 Al, Nov 19, 2009.
2. Sr. Michael John Collins (CEM Corporation), Microwave-assisted preparation of a sample for chromatography, EP1628131 Al, 22 Feb 2006.
3. Kevin D. Belfield, Ciceron O. Yanez, Microwave-assisted formation of sulfonium photoacid generators, US8192590 Bl,5Jun2012.
4. Jacob Westman, Preparation and use of ionic liquids in microwave-assisted chemical transformations US 6596130 B2, 22 Jul 2003.
5. Arun Kumar Sinha, Bhupendra Prasad Joshi, Anuj Sharma, Microwave induced process for the preparation of substituted 4-vinylphenols US 6989467 B2, 24 jan 2006.
6. Johan Ulin, Per-Gunnar Eriksson, Fredrik Ekdahl, Vessel for performing microwave-assisted chemistry on small volume so freagents US 20060147352 Al, 6 Jul 2006.
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Title of invention: Microwave induced synthesis of Benzoyl propionic acid and their
derivatives
WE Claims:
1. Method of synthesis:
Conventional method is replaced by green method i.e microwave irradiation used for synthesis of P-Benzoyl Propanoic Acid via friedel craft reaction. In conventional method, energy provide by means of thermal heating change by microwave irradiation which implies activation of reactant molecules to achieve better reactivity
2. Single set up:
In conventional method, heating menthal, water condenser, source of water and glassware's are required to prepare product is replaced by single set up like microwave.
3. Absolute maintain of anhydrous condition:
In conventional synthesis to maintain anhydrous condition required guard tube (filling with cotton) but in microwave irradiation itself in anhydrous condition
4. Easy to moderate reaction:
In conventional set up for moderation of reaction is difficult because there is large set up which is difficult to seprate in running condition to take out a small amount of reaction mixture to load on thin layer chromatography (TLC)
5. Environmental Benign:
In conventional method, condensation of reaction solvent is required to maintain the volume of solvent till the completion of reaction by circulation of water in water condenser. So wastage of water thought in 45 minutes course of reaction is overcome by microwave irradiation method there is no such type of requirement is required.
6. Reduce number of steps in work up of reaction:
In conventional method, synthesis of P-benzoyl propionic acid in five steps. In first step, in round bottom flask mixtire of benzene, succinic anhydride and catalyst like A1C13 condensation trough thermal heating. Second step hydrolysis by acute amount of water and concentrated HC1. In third step distillation of benzene. Fourth step Na benzene and succinic anhydride are condensed by friedel craft reaction
7. Reduce time
It brings up a huge reduction in the rate determining step. The time is reduced to 1 min to 5 min. It is time consuming and laborious process to prepare products and their work up required huge time. Microwave irradiation is new tool for green chemistry to find simplest productivity and their atomicity
8. Energy:
The heating with heating menthal and burner brought the distribution of heat energy into heating of reacting mixture containing vessel, whereas the microwave provides all the energy to the reaction mixture without wasting it in the unwanted things like heating of vessel. Due to the investment of whole energy for the conversion of the moiety into product
9. Minimum quantity of reactant and catalyst required
In microwave assisted reaction, efficient amount of anhydrous condition is maintained. Optimization of minimum quantity of reactants with catalyst ratio is 3:4.
10. Yield of product:
In microwave induced organic synthesis increased yield due to absolute maintains anhydrous condition, lesser the steps in workup reactions and single set up yield 97% of product.

Title of invention: Microwave induced synthesis of Benzoyl propionic acid and
their derivatives
Rajdip Utanea & Sujata Deob
a-Sant Gadge Maharaj Mahavidyalaya Suraj Nagar, Hingna, Nagpur-441110
b-Govt. Institute of Science, R.T. Road, Civil line, Nagpur-440001
Email id: raj.cheniworld @ gmail.com