Title of Invention

A PROCESS TO CONVERT ETHYL PARABEN IN TO PARA ETHOXY ETHYL BENZOATE (PEEB)

Abstract

The present invention relates to the synthesis of para ethoxy ethyl benzoate by the etherification of ethyl paraben by diethyl sulphate in the presence of solvent water, quaternary ammonium salt and base like sodium hydroxide, potassium hydroxide or lithium hydroxide by addition of carbonates at least maintaining stage and isolating the inorganic sulphate and ethyl alcohol from mother liquor and recycle of the ethyl alcohol in ethyl paraben formation which is the basic material of this process.

Full Text

FORM - 2 THE PATENT ACT, 1970 (39 of 1970) PROVISIONAL SPECIFICATION [SECTION 10 ; RULE 13] A PROCESS TO CONVERT ETHYL PARABEN IN TO PARA ETHOXY ETHYL BENZOATE (PEEB). GUJARAT ORGANICS LIMITED, AN INDIAN COMPANY INCORPORATED UNDER THE COMPANIES ACT, 1956 HAVING ITS OFFICE AT PLOT NO 127/1, G.I.D.C. ESTATE, ANKLESHWAR - 393 002, DIST BHARUCH, GUJARAT STATE, INDIA. THE FOLLOWING SPECIFICATIONS PARTICULARLY DESCRIBES THE NATURE OF THIS INVENTION :- The present invention relates to a new process of Para Ethoxy Ethyl Benzoate (PEEB), Wherein Ethyl Paraben is used as the starting material. The prior art Indian Patent No 197698 (10/03/2003), Patent No 203929 (10/03/2003) and Patent application No 470/mum/2003 discloses the process of Para Ethoxy Ethyl benzoate wherein in Patent No 197698 the Para Ethoxy Ethyl Benzoate is prepared in two steps while in Patent application No 203929 p-Hydroxy Benzoic Acid is reacted with Diethyl Sulphate in the presence of Sodium Carbonate, Benzyl Chloride and Triethyl Amine in Xylene medium (Dry Process). The residual Di Ethyl Sulphate in commercial Para Ethoxy Ethyl Benzoate is typically with in the range of 5 to 10 ppm. The 3rd Patent application of Para Ethoxy Ethyl benzoate (470/mum/2003) describes the preparation of Para Ethoxy Ethyl Benzoate by reacting p-Hydroxy Benzoic Acid, Diethyl Sulphate, and Quaternary Ammonium Salt in the presence of alkali Hydroxide solution in water (Wet Water Process) In the prior processes: 1) Diethyl Sulphate consumption in the reaction is high and there is no report of recovery of derivatives of Diethyl Sulphate from Mother Liquor and their use in the processes The present invention discloses the synthesis, characterization of Para Ethoxy Ethyl Benzoate. The present compound has commercial application as external electron donor in Poly Propylene manufacturing. The present invention discloses the recovery of Ethanol from the Mother Liquor of Para Ethoxy Ethyl Benzoate and its use in the synthesis of Ethyl Paraben and conversion of Ethyl Paraben into Para Ethoxy Ethyl Benzoate. The benefits are following 1. The byproduct Ethanol recovered from Mother Liquor is utilized in the synthesis of Para Ethoxy Ethyl Benzoate. 2. The effluent load on effluent treatment plant is reduced as we recover the Ethyl Alcohol and reuse it in the process. 3. The production cost of PEEB is reduced because Diethyl Sulphate the major raw material in the synthesis of Para Ethoxy Ethyl Benzoate consumption is reduced to 25% - 30% of existing consumption Description of the invention The present invention involves the conversion of p-Hydroxy Benzoic Acid in to Ethyl Paraben by using the recovered Ethanol from the Mother Liquor of Para Ethoxy Ethyl Benzoate in the presence of phase transfer catalyst aryl Sulphonic Acid. After the formation of Ethyl Paraben, Ethanol is distilled out and water is added in to the residue followed by the addition of Sodium Hydroxide, phase transfer catalyst and Diethyl Sulphate to convert Ethyl Paraben in to Para Ethoxy Ethyl Benzoate. The best advantage of the invention is reduction in the consumption quantities of Diethyl Sulphate to 70% because 30% job is done by the recovered Ethanol from the Mother Liquor. 2) The second advantage of the invention is reduction of the effluent load in Mother Liquor for treatment and to recycle the recovered Ethyl Alcohol to form PEEB using the above invention According to this invention the process for manufacturing Para Ethoxy Ethyl Benzoate using Ethyl Paraben as starting raw material, Diethyl Sulphate and quaternary Ammonium salt in the presence of an alkali hydroxide solution in water + alkali Carbonate in water followed by the Ethanol recovery from the Mother Liquor of PEEB. In the said process the quaternary ammonium salt is either Triethyl Benzyl Ammonium Chloride, Benzyl Tributyl Ammonium Bromide, Benzyl Trimethyl Ammonium iodide, Benzyl Trimethyl Ammonium Chloride, Benzyl Trimethyl Ammonium Bromide; said Alkali hydroxide (i) is selected from Sodium Hydroxide or Potassium hydroxide or Lithium Hydroxide; said Alkaline Carbonate used as Sodium Carbonate, Potassium Carbonate, Lithium Carbonate and Magnesium Carbonate. In the said process the pH of said reaction at step : 2 is maintained in the range of 12.5 to 1 3.5. Further In the said process reaction of Ethyl Paraben and Diethyl Sulphate is conducted in the temperature range of 30°C-55°C. Still further, in the said process for preparing Para Ethoxy Ethyl Benzoate, Para Ethoxy Ethyl Benzoate is Diethyl Sulphate free and the resultant product is purified by distillation. In the said process for preparing Para Ethoxy Ethyl Benzoate reaction solvent is water and moisture content of said distilled Para Ethoxy Ethyl Benzoate is in the range of 135 to 180 ppm. Detailed description of the invention The present invention involves the conversion of p-Hydroxy Benzoic Acid in to Ethyl Paraben by using the recovered Ethanol and conversion of Ethyl Paraben in to Para Ethoxy Ethyl Benzoate in the presence of quaternary Ammonium salts and Diethyl Sulphate at controlled pH. The single pot synthesis takes place in two steps 1. Conversion of COOH group to Ethyl Paraben (Esterification) 2. Ethyl Paraben -OH Etherification. Esterification of COOH group is performed in the presence of Ethanol and aryl Sulphonic Acid after the reaction Ethanol is recovered for drying and reuse. Then to the reaction mass water is added followed by the addition of alkali Hydroxide and quaternary Ammonium Salt followed by the slow addition of Diethyl Sulphate. The progress of the reaction is monitored on TLC and continued till Ethyl Paraben is absent. The pH range maintained is 12.5 - 13.5 till every thing get converted in to Para Ethoxy Ethyl Benzoate. After the completion of the reaction, water is added. The oily organic layer is separated and washed with water. The water traces are removed by vacuum drying at 50°C - 55°C and the product is purified and isolated by high vacuum distillation (130°C/ 1mm of Hg). The following chemical reaction illustrate the invention The invention will now be described with references to the following examples which are only illustrative and in no way limit to the scope of the invention EXAMPLE : 1 Charge Ethyl Paraben 1.0Kg, water 1.0Lit, followed by the slow addition of Sodium Hydroxide 0.300 Kg. Then cool the content to 30°C. Then add tetra Butyl Ammonium Bromide (TBAB) dissolved in water at 30°C. Then start Diethyl Sulphate addition 1.2 Kg below 30°C with stirring. After completion of DES addition stir the reaction mass below 30°C for 16 hrs and maintain the pH of reaction mass to 12.5 to 13.5. Then check the TLC for p-Hydroxy Benzoic Acid, Ethyl Paraben and 4-Ethoxy Benzoic Acid content and these all impurities should be less than 0.5% or nil. If present add 0.2 Kg. Of Sodium hydroxide dissolve in 0.2Lit of water and stirrer the mass for another 4 hrs. Then charge 0.1 50 Kg. Sodium Carbonate and raise the temperature to 30°C to 40±5°C and maintain for 6.0 hrs. Now TLC shows PEEB spot. Separate the Para Ethoxy Ethyl Benzoate as oily layer. Wash the Para Ethoxy Ethyl Benzoate with water. Dry the crude Para Ethoxy Ethyl Benzoate under vacuum at 50°C-55°C and purify the same by vacuum distillation at 130°C/ 1mm of Hg. Distilled PEEB = 1.07Kg. Yield = 92% (Theory) Diethyl Sulphate (By GC) = Nil Moisture Content = 150 ppm EXAMPLE : 2 Charge Ethyl Paraben 1.0Kg, water 1.0Lit, followed by the slow addition of Sodium Hydroxide 0.300 Kg. Then cool the content to 30°C. Then add tetra Butyl Ammonium Iodide (TBAI) dissolved in water at 30°C. Then start Diethyl Sulphate addition 1.2 Kg below 30°C with under stirring. After completion of DES addition stir the reaction mass below 30°C for 16 hrs and maintain the pH of reaction mass to 12.5 to 13.5. Then check the TLC for p-Hydroxy Benzoic Acid, Ethyl Paraben and 4-Ethoxy Benzoic Acid content and these all impurities should be less than 0.5% or nil. If present add 0.2 Kg. Of Sodium hydroxide dissolve in 0.2Lit of water and stir the mass for another 4 hrs. Then charge 0.150 Kg. Sodium Carbonate and raise the temperature to 30°C to 40±5°C and maintain for 6.0 hrs. Now TLC shows PEEB spot. Separate the Para Ethoxy Ethyl Benzoate as oily layer. Wash the Para Ethoxy Ethyl Benzoate with water. Dry the crude Para Ethoxy Ethyl Benzoate under vacuum at 50°C-55°C and purified the same by vacuum distillation at 130°C/ 1mm of Hg. Distilled PEEB =1.07Kg. Yield = 92% (Theory) Diethyl Sulphate (By GC) = Nil Moisture Content = 180 ppm EXAMPLE : 3 Charge Ethyl Paraben 1.0Kg, water 1.0Lit, followed by the slow addition of Sodium Hydroxide 0.300 Kg. Then cool the content to 30°C. Then add Triethyl Benzyl Ammonium Chloride dissolved in water at 30°C. Then start Diethyl Sulphate addition 1.2 Kg below 30°C with under stirring. After completion of DES addition stir the reaction mass below 30°C for 16 hrs and maintain the pH of reaction mass to 12.5 to 13.5. Then check the TLC for p-Hydroxy Benzoic Acid, Ethyl Paraben and 4-Ethoxy Benzoic Acid content and these all impurities should be less than 0.5% or nil. If present add 0.2 Kg. Of Sodium hydroxide dissolve in 0.2Lit of water and stirrer the mass for another 4 hrs. Then charge 0.1 50 Kg. Sodium Carbonate and raise the temperature to 30°C to 40±5°C and maintain for 6.0 hrs. Now TLC shows PEEB spot. Separate the Para Ethoxy Ethyl Benzoate as oily layer. Wash the Para Ethoxy Ethyl Benzoate with water. Dry the crude Para Ethoxy Ethyl Benzoate under vacuum at 50°C-55°C and purified the same by vacuum distillation at 130°C/ 1mm of Hg. Distilled PEEB = 1.07Kg. Yield = 92% (Theory) Diethyl Sulphate (By CC) = Nil Moisture Content =140ppm EXAMPLE : 4 Charge Ethyl Paraben 1.0Kg, water 1.0Lit, followed by the slow addition of Sodium Hydroxide 0.300 Kg. Then cool the content to 30°C. Then add tetra Butyl Ammonium Hydrogen Sulphate dissolved in water at 30°C. Then start Diethyl Sulphate addition 1.2 Kg below 30°C with under stirring. After completion of DES addition stir the reaction mass below 30°C for 16 hrs and maintain the pH of reaction mass to 12.5 to 13.5. Then check the TLC for p-Hydroxy Benzoic Acid, Ethyl Paraben and 4-Ethoxy Benzoic Acid content and these all impurities should be less than 0.5% or nil. If present add 0.2 Kg. Of Sodium hydroxide dissolve in 0.2Lit of water and stir the mass for another 4 hrs. Then charge 0.150 Kg. Sodium Carbonate and raise the temperature to 30°C to 40±5°C and maintain for 6.0 hrs. Now TLC shows PEEB spot. Separate the Para Ethoxy Ethyl Benzoate as oily layer. Wash the Para Ethoxy Ethyl Benzoate with water. Dry the crude Para Ethoxy Ethyl Benzoate under vacuum at 50°C-55°C and purified the same by vacuum distillation at 130°C/ 1mm of Hg. Distilled PEEB =1.07Kg. Yield = 92% (Theory) Diethyl Sulphate (By GC) = Nil Moisture Content =140ppm EXAMPLE : 5 Charge Ethyl Paraben 1.0Kg, water 1.0Lit, followed by the slow addition of Potassium Hydroxide 0.430 Kg. Then cool the content to 30°C. Then add KOH Base dissolved in water at 30°C. Then start Diethyl Sulphate addition 1.2 Kg below 30°C with under stirring. After completion of DES addition stir the reaction mass below 30°C for 16 hrs and maintain the pH of reaction mass to 12.5 to 13.5. Then check the TLC for p-Hydroxy Benzoic Acid, Ethyl Paraben and 4-Ethoxy Benzoic Acid content and these all impurities should be less than 0.5% or nil. If present add 0.2 Kg. Of Sodium hydroxide dissolve in 0.2Lit of water and stirrer the mass for another 4 hrs. Then charge 0.1 50 Kg. Sodium Carbonate and raise the temperature to 30°C to 40±5°C and maintain for 6.0 hrs. Now TLC shows PEEB spot. Separate the Para Ethoxy Ethyl Benzoate as oily layer. Wash the Para Ethoxy Ethyl Benzoate with water. Dry the crude Para Ethoxy Ethyl Benzoate under vacuum at 50°C-55°C and purified the same by vacuum distillation at 130°C/ 1mm of Hg. Distilled PEEB =1.07Kg. Yield = 92% (Theory) Diethyl Sulphate (By GC) = Nil Moisture Content =140ppm EXAMPLE : 6 Charge Ethyl Paraben 1.0Kg, water 1.0Lit, followed by the slow addition of Lithium Hydroxide 0.220 Kg. Then cool the content to 30°C. Then add LiOH Base dissolved in water at 30°C. Then start Diethyl Sulphate addition 1.2 Kg below 30°C with under stirring. After completion of DES addition stir the reaction mass below 30°C for 16 hrs and maintain the pH of reaction mass to 12.5 to 13.5. Then check the TLC for p-Hydroxy Benzoic Acid, Ethyl Paraben and 4-Ethoxy Benzoic Acid content and these all impurities should be less than 0.5% or nil. If present add 0.2 Kg. Of Sodium hydroxide dissolve in 0.2Lit of water and stirrer the mass for another 4 hrs. Then charge 0.1 50 Kg. Sodium Carbonate and raise the temperature to 30°C to 40±5°C and maintain for 6.0 hrs. Now TLC shows PEEB spot. Separate the Para Ethoxy Ethyl Benzoate as oily layer. Wash the Para Ethoxy Ethyl Benzoate with water. Dry the crude Para Ethoxy Ethyl Benzoate under vacuum at 50°C-55°C and purified the same by vacuum distillation at 130°C/ 1mm of Hg. Distilled PEEB =1.07Kg. Yield = 92% (Theory) Diethyl Sulphate (By GC) = Nil Moisture Content = 135 ppm

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2100-mum-2007-abstract(13-10-2008).pdf

2100-MUM-2007-ABSTRACT(2-7-2012).pdf

2100-MUM-2007-ANNEXURE 1(17-9-2013).pdf

2100-mum-2007-claims(13-10-2008).pdf

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2100-MUM-2007-CORRESPONDENCE(8-6-2009).pdf

2100-mum-2007-correspondence-received.pdf

2100-mum-2007-description (provisional).pdf

2100-mum-2007-description(complete)-(13-10-2008).pdf

2100-MUM-2007-FORM 13(13-7-2012).pdf

2100-MUM-2007-FORM 18(8-6-2009).pdf

2100-mum-2007-form 2(13-10-2008).pdf

2100-mum-2007-form 2(title page)-(13-10-2008).pdf

2100-MUM-2007-FORM 2(TITLE PAGE)-(2-7-2012).pdf

2100-mum-2007-form 2(title page)-(provisional)-(24-10-2007).pdf

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