Title of Invention

A PROCESS FOR SYNTHESIS OF PARA PROPOXY ETHYL BENZOATE

Abstract The present invention relates to a new product para propoxy ethyl benzoate and its synthesis, which comprises the process of etherification of ethyl paraben in various solvents using n-propyl iodine or n-propyl bromide as etherification agent in the presence of bases like sodium hydroxide or potassium hydroxide and isolating the inorganic halides by filtration and removal of unreacted ethyl paraben after the recovery of the solvent by distillation and washing with alkali solution.
Full Text FORM - 2
THE PATENT ACT. 1970 (39 of 1970)
PROVISIONAL SPECIFICATION
[SECTION 10 ; RULE 1 3]
PARA PROPOXY ETHYL BENZOATE AND SYNTHESIS THEREOF
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 product, Viz Para Propoxy Ethyl
Benzoate or p - n - Propoxy Ethyl Benzoate (PPEB), its synthesis and its
purification.
The present invention discloses the synthesis, characterization of Para
Propoxy Ethyl Benzoate. The present compound has commercial
application as external electron donor in Poly Propylene
manufacturing.
The present invention also discloses the synthesis of Para Propoxy
Ethyl Benzoate by esterification of p-Hydroxy Benzoic Acid with
Ethanol in the presence of Sulphonic Acid followed by recovery of
excess ethanol by distillation. The residual material is purified in water
by neutralization using a base Viz Sodium Bicarbonate / Sodium
Hydroxide / Potassium Hydroxide / Sodium Carbonate in the dilute
solution in water.
In the preferred embodiment, the process of esterification is carried
out in the presence of an Aryl Sulphonic Acid e.g. Para Toluene
sulphonic Acid. The process of esterification can also be carried out in
the presence of an Alkyl Sulphonic Acid e.g. Methane Sulphonic Acid.
Hydrochloric Acid can also be used as a catalyst in the process of
esterification, polymer Sulphonic Acid e.g. Ion Exchange Resins like
Indion 850/ Duolite 368 can also be used as a catalyst in the process
of esterification.
Dry Ethyl Paraben obtained from the above process is etherified using
halogenated Propyl derivatives (CI, Br and I) in the presence of a base
such as NaOH or KOH in a solvent VizO.D.C.B., Methyl Iso Butyl Ketone,
Diethyl Formamide and Dimethyl Formamide.
According to this invention, Para Propoxy Ethyl Benzoate has the
following structure





Further according to this invention, the process for manufacturing Para Propoxy Ethyl Benzoate comprises of the following steps

(a) Etherification of Ethyl Paraben in liquid Formamide reacting it with n - Propyl Halide (Br or I) in the presence of Alkali Hydroxide.
(b) Isolation of resulting inorganic Halide by filtration.
(c) Recovery of solvent by distillation.
(d) Removal of unreacted Ethyl Paraben.
In the above step (a) firstly Ethyl Paraben is dissolved in liquid
Formamide; secondly alkali Hydroxide is slowly added to the above
solution in the first sub step under stirring; thirdly n - Propyl Halide is
added to the above solution in the second sub step under stirring.
The reaction temperature is maintained between 30°C - 75°C
throughout.
Further in the said step liquid Formamide is N, N- Dimethyl
Formamide or N, N - Diethyl Formamide or Methyl Iso Butyl Ketone or
Ortho Di Chloro Benzene; etherification reagent is n - Propyl Bromide
or n - Propyl Iodide; and moisture content of said distilled Para
Propoxy Ethyl Benzoate is in the range of 1 50 -200 ppm.
In the step (d) unreacted Ethyl Paraben is removed by washing the
reaction mass with alkali hydroxide or alkali carbonate solution or
alkali bicarbonate solution and the resultant product is purified by
distillation.
The following reaction illustrates the invention









The present invention is illustrated with the following additional examples. The above stated reaction as also below examples are only illustrative and in no way limit the scope of invention.
EXAMPLE - 1
Charge N, N - Dimethyl Formamide (1.88 Kg.), Ethyl Paraben (2.0 Kg.) followed by the addition of Sodium Hydroxide (0.480 Kg.). Stir the contents for 4.0 hours. Then add n - Propyl Bromide (2.38Kg.) to convert Ethyl Paraben into Para Propoxy Ethyl Benzoate. Maintain the reaction at 30°C - 75°C to complete the reaction. Monitor the progress of the reaction on TLC. After completion of the reaction filter the solid Sodium Bromide and collect the Mother Liquor containing N, N -Dimethyl Formamide and Para Propoxy Ethyl Benzoate. Distill out the N, N - Dimethyl Formamide under vacuum at 95°C - 100°C/0.5 - 1.0 mm of Hg and recover N, N - Dimethyl Formamide (1.78 Kg.) Add water to the residue. Separate the upper organic layer. Wash the organic layer with 5% KOH solution or 5% NaHCO3 solution or 5% Sodium Carbonate solution. Then wash the organic layer with water (250 ml). Distill the organic layer under vacuum at 110°C - 120°C / 0.5 - 1.0 mm of Hg.
Weight of Para Propoxy Ethyl Benzoate = 2.00 Kg.
Yield = 83.19% (Theory)


G.C. Purity = 99.4%
Para Propoxy Benzoic Acid = 0.04 %
Moisture Content = 200 ppm
EXAMPLE - 2
Charge N, N - Diethyl Formamide (1.88 Kg.), Ethyl Paraben (2.0Kg.) followed by the addition of Potassium Hydroxide (0.680 Kg.). Stir the contents for 6.0 hours. Then add n - Propyl Bromide (2.38 Kg.) to convert Ethyl Paraben to Para Propoxy Ethyl Benzoate. Maintain the reaction at 30°C - 75°C to complete the reaction. Monitor the progress of the reaction on TLC. After completion of the reaction filter the solid Potassium Bromide and collect the Mother Liquor containing N, N - Diethyl Formamide and Para Propoxy Ethyl Benzoate. Distill out the N, N - Diethyl Formamide under vacuum at 95°C -100°C/0.1 - 1.0 mm of Hg and recover N, N - Diethyl Formamide (1.8 Kg. approx.). Add water to the residue. Separate the upper organic layer. Then wash the organic layer with 5% KOH solution or 5% NaHC03 solution or 5% Sodium Carbonate solution (200 ml). Then wash the organic layer with water (200 ml). Distill the organic layer under vacuum at 110°C - 1 20°C / 0.1 -1.0 mm of Hg.
Weight of Para Propoxy Ethyl Benzoate = 2.25 Kg.
% Yield = 90% (Theory)
G.C. Purity = 99.3%
Para Iso Propoxy Benzoic Acid = 0.03%
Moisture Content = 150 ppm
EXAMPLE - 3
Charge N, N - Diethyl Formamide (1.9 Kg.), Ethyl Paraben (2.0 Kg.) followed by the slow addition of Sodium Hydroxide (0.480 Kg.). Stir the contents for 6.0 hours. Then add n - Propyl Bromide (2.38Kg.) to convert Ethyl Paraben to Para Propoxy Ethyl Benzoate. Maintain the reaction at 30°C - 75°C to complete the reaction. Monitor the progress of the reaction on TLC. After completion of the reaction filter the solid Sodium Bromide and collect the Mother Liquor containing N, N -Diethyl Formamide and Para Propoxy Ethyl Benzoate. Distill out the N, N - Diethyl Formamide under vacuum at 100°C / 1.0 mm of Hg and recover N, N - Diethyl Formamide (1.7 Kg.) Add water to the residue.


Separate the upper organic layer. Wash the organic layer with 5% NaOH solution or 5% NaHC03 solution or 5% Sodium Carbonate solution or 5% KOH solution (200 ml). Then wash the organic layer with water (250 ml). Distill the organic layer under vacuum at 110°C - 120°C / 0.5 -1.0 mm of Hg.
Weight of Para Propoxy Ethyl Benzoate = 2.30 Kg.
Yield = 92% (Theory)
G.C. Purity = 99.3%
Para Iso Propoxy Benzoic Acid = 0.03%
Moisture Content = 1 50 ppm
EXAMPLE - 4
Charge N, N - Diethyl Formamide (1.9 Kg.), Ethyl Paraben (2.0 Kg.) followed by the addition of Sodium Hydroxide (0.480 Kg.). Stir the contents for 4.0 hours. Then add n - Propyl Iodide (3.0 Kg.) to convert Ethyl Paraben to Para Propoxy Ethyl Benzoate. Maintain the reaction at 30°C - 75°C to complete the reaction. Monitor the progress of the reaction on TLC. After completion of the reaction filter the solid Sodium Iodide and collect the Mother Liquor containing N, N - Diethyl Formamide and Para Propoxy Ethyl Benzoate. Distill out the N, N -Diethyl Formamide under vacuum at 95°C -100°C/ 10 mm of Hg and recover N, N - Diethyl Formamide (1.70 Kg. app.). Add water to the residue separate the upper organic layer. Then wash the organic layer with 5% NaOH solution or 5% NaHC03 solution or 5% Sodium Carbonate solution or 5% KOH solution (200 ml). Then wash the organic layer with water (250 ml). Distill the organic layer under vacuum at 110°C - 1 20°C / 0.5 - 1.0 mm of Hg.
Weight of Para Propoxy Ethyl Benzoate = 2.2 Kg.
% Yield = 88% (Theory)
G.C. Purity = 99.3%
Para Iso Propoxy Benzoic Acid = 0.03%
Moisture Content =180 ppm
EXAMPLE - 5


Charge Ortho Di Chloro Benzene (1.9 Kg.), Ethyl Paraben (2.0 Kg.) followed by the slow addition of Sodium Hydroxide (0.480 Kg.). Stir the contents for 6.0 hours. Then add n - Propyl Bromide (2.38 Kg.) to convert Ethyl Paraben to Para Propoxy Ethyl Benzoate. Maintain the reaction at 30°C - 75°C to complete the reaction. Monitor the progress of the reaction on TLC. After completion of the reaction filter the solid Sodium Bromide and collect the Mother Liquor containing Ortho Di Chloro Benzene and Para Propoxy Ethyl Benzoate. Distill out the Ortho Di Chloro Benzene under vacuum at 100°C /0.1 - 1.0 mm of Hg and recover Ortho Di Chloro Benzene (1.70 Kg. app.). Then add water (200 ml) to the residue separate the upper organic layer. Then wash the organic layer with 5% NaOH solution (200 ml). Then wash the organic layer with water (250 ml). Distill the organic layer under vacuum at 110°C - 120°C / 0.1 - 1.0 mm of Hg.
Weight of Para Propoxy Ethyl Benzoate = 2.37 Kg.
% Yield = 94.8% (Theory)
G.C. Purity = 99.20%
Para Iso Propoxy Benzoic Acid = 0.04%
Moisture Content = 1 50 ppm
EXAMPLE - 6
Charge Methyl Iso Butyl Ketone (1.9 Kg.), Ethyl Paraben (2.0 Kg.) followed by the slow addition of Sodium Hydroxide (0.480 Kg.). Stir the contents for 6.0 hours. Then add n - Propyl Bromide to convert Ethyl Paraben to Para Propoxy Ethyl Benzoate. Maintain the reaction at 30°C - 75°C to complete the reaction. Monitor the progress of the reaction on TLC. After completion of the reaction, filter the solid Sodium Bromide and collect the Mother Liquor containing Methyl Iso Butyl Ketone and Para Propoxy Ethyl Benzoate. Distill out the Methyl Iso Butyl Ketone (1.70 Kg. approx.). Add water to the residue. Separate the upper organic layer. Then wash the organic layer with 5% NaOH solution (200 ml). Then wash the organic layer with water (200 ml). Distill the organic layer under vacuum at 110°C - 120°C / 0.1 - 1.0 mm of Hg.
Weight of Para Propoxy Ethyl Benzoate = 2.30 Kg.
% Yield - 92% (Theory)
G.C. Purity = 99.4%


Para Iso Propoxy Benzoic Acid = 0.02%
Moisture Content = 175 ppm
ADVANTAGES
1. The present inventions synthesizes new product Para Propoxy Ethyl Benzoate with very low Para Propoxy Benzoic Acid impurity (less than 0.1%)
2. The present invention synthesizes Para Propoxy Ethyl Benzoate of 99.3% to 99.4% G.C. Purity.
3. The present invention is an economical method for producing the new product Para Propoxy Ethyl Benzoate.



Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=dTIJ4KBBV/QJCKramPuZ2Q==&loc=vsnutRQWHdTHa1EUofPtPQ==


Patent Number 268998
Indian Patent Application Number 2101/MUM/2007
PG Journal Number 40/2015
Publication Date 02-Oct-2015
Grant Date 28-Sep-2015
Date of Filing 24-Oct-2007
Name of Patentee GUJARAT ORGANICS LTD.
Applicant Address PLOT NO. 127/1,GIDC ESTATE,ANKLESHWAR 393002,DIST BHARUCH
Inventors:
# Inventor's Name Inventor's Address
1 ARVIND SHAH PLOT NO. 127/1, GIDC ESTATE, ANKLESHWAR 393002, DIST BHARUCH
2 PATHAK RAJESH KUMAR PLOT NO. 127/1, GIDC ESTATE, ANKLESHWAR 393002, DIST BHARUCH
PCT International Classification Number C07C67/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA