Title of Invention	PROCESS FOR MANUFACTURING 4-ALKYL RESORCINOL DERIVATIVES
Abstract	The present invention relates to a process of manufacturing 4-alkyl resorcinol derivatives. More specifically, the present invention relates to a process of manufacturing 4-alkyl resorcinol derivatives by acetylation of 4-acyl resorcinol, followed by hydrogenation and hydrolysis.

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J6912 FORM - 2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See Section 10 and Rule 13) PROCESS FOR MANUFACTURING 4-ALKYL RESORCINOL DERIVATIVES HINDUSTAN LEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India The following specification particularly describes the invention and the manner in which it is to be performed. J6912(C) PROCESS FOR MANUFACTURING 4-ALKYL RESORCINOL DERIVATIVES FIELD OF THE INVENTION The present invention relates to a process of manufacturing 4-alkyl resorcinol derivatives. More specifically, the present invention relates to a process of manufacturing 4-alkyl resorcinol derivatives by acetylation of 4-acyl resorcinol, followed by hydrogenation and hydrolysis. BACKGROUND AND PRIOR ART Resorcinol and its derivatives have a wide variety of applications. The largest consumption of resorcinol is in the tire industry where the preferred hardening resins are based on resorcinol. Another value-added application of resorcinol and its derivatives is in cosmetic products. Some compounds like 2, 4 -dihydroxyacetophenone have been used in sun-protective applications or compositions for providing sun protection. Alkyl and aryl resorcinols are reported to possess valuable therapeutic and antiseptic properties. In particular, 4-alkyl resorcinols are reported to have skin-beautifying effect and low toxicity and irritation when applied on to human skin. Alkyl resorcinols like 4-n-butyl resorcinol have been used in skin creams and lotions which are claimed to have good bleaching and anti-microbial effect, as well as skin depigmentation properties. Synthetic Communications 15 (14), 1315-24 (1985) describes a process to prepare 4-ethyl resorcinol by reaction of 2,4 - dihydroxy acetophenone and sodium borocyano hydride in methanol medium. This process is difficult to implement on industrial scale and not cost-effective as sodium boro cyano hydride is not a catalyst but one of the reactants. Therefore, the reaction 1 e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C) produces a large amount of by-products, which are difficult to dispose of in an environmentally safe way. Zinc and mercuric compounds have been used to prepare compounds within the scope of general formula I, starting with compounds of formula A. J. Am Chem. Soc, 52, 4866-82 (1930) reports a process where 4-ethyl resorcinol is prepared in 82% yield by reaction of 2,4-dihydroxy acetophenone with Zn and mercuric chloride in hydrochloric acid solution. Rec. trav. Chim. 50, 848-50 (1931) describes preparation of compound of general formula I, where R is a straight chain alkyl group with a carbon chain length of 5 in 84% yield by reaction of the corresponding ketone in the presence of Zn and dilute hydrochloric acid. The same product has been reported to be prepared in 71% yield in Acad. Rep. Populare Romine, "Studii cercetari chim.," 3, 13-18 (1955) by using Zn and mercuric chloride as the catalysts. The above methods are industrially not viable as the process comprises use of toxic and environmentally unfriendly chemicals containing mercury. Tr. Tallin. Politekhn. In-ta (543) 78-83 (1983) reports the preparation of 4-ethyl resorcinol from 2,4-dihydroxyacetophenone in the presence of hydrochloric acid which is a non-catalytic reaction. The maximum yield reported is only 42% and therefore is not industrially workable. Australian Journal of Chemistry. 22(3), 601-5 (1969) describes the preparation of 4-ethyl resorcinol by reaction of 2,4-dihydroxyacetophenone with sodium borohydride which is a non-catalytic reaction. This reaction is not an industrially feasible reaction due to the large amount of sodium borohydride that needs to be used and the problems of downstream purification. Compound of formula I, but with a much higher carbon chain length of 14 has been reported in Journal of Medicinal Chemistry 29 (5), 606-11 (1986) to be prepared by the reaction of the corresponding compound of formula A with hydrogen gas and acetic acid using palladium as the catalyst in ethanol medium. 2 e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C) J. Am Chem. Soc. (1939), 61, 249-54 describes that reduction of dihydroxy acetophenone with a palladium catalyst gave only a poor yield of 4-ethyl resorcinol and so the study was not extended. There is thus a need for an industrially viable process to prepare compounds of general formula I in high yields and purity. (I) The present inventors have found that compounds of general formula I can be prepared in very high yields and purity by acetylating compounds of general formula A, (A) followed by reacting the acetylated material with a source of hydrogen in the presence of Palladium catalyst on Carbon substrate. These steps are followed by hydrolysis in acidic media at or above room temperature. 3 e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C) SUMMARY OF THE INVENTION An object of the present invention is to prepare compounds of general formula I in high yields and purity. It is a further object of the present invention to prepare compounds of general formula I, by using chemicals/ raw materials that are readily available at economical price and are easily recycled for better economy. It is a yet another object of the present invention to prepare compounds of general formula I by a process that is efficient and does not create by-products, which are difficult to separate or are environmentally unfriendly. Other objects of the present invention will become apparent with reference to the present specification. The present invention relates to a novel process for the preparation of compounds of general formula I in high yields and purity: (I) where R is hydrogen or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, which is either straight chain, branched or cyclic, with or without hetero-atoms (oxygen, nitrogen or sulfur), anywhere in the chain or ring, 4 e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C ) starting with compounds of general formula A: OH (A) The invention is particularly useful for preparing compounds for preparation of cosmetic compositions, particularly skin lightening cosmetic compositions. According to a preferred aspect of the invention there is provided a process for the preparation of compound of general formula I, comprising acetylating compound of general formula A, followed by reacting the acetylated material with hydrogen gas at pressures in the range of less than about 700 psig, preferably about 50 to about 600 psig, more preferably about 100 psig. Hydrogenation is in the presence of palladium catalyst, preferably, Palladium on Carbon catalyst, which is recyclable. Preferably, palladium content is not greater than 10% by weight of the catalyst. The Hydrogenation reaction takes place at a pH below 7.0 and temperature of below 50 deg. C, preferably at room temperature. Hydrogenation is followed by hydrolysis in acidic media, preferably aqueous acetic acid, at or above 23 deg. C, preferably about 23 to about 150 deg. C. e:\data\word\patents\Resorcinol\2-Cornpletion4-8-05.doc J6912(C) DETAILED DESCRIPTION OF THE INVENTION The present invention provides for a novel process to prepare compounds of general formula I, starting with compounds of general formula A: (I) where R is hydrogen or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, which is either straight chain, branched or cyclic, with or without hetero-atoms (oxygen, nitrogen or sulfur) anywhere in the chain or ring. Starting materials are compounds of general formula A: (A) The process could also be carried out starting with precursors of compounds of general formula A. Reactions well known in the art could be employed to first prepare compounds of general formula A, such Friedel Krafts acylation of resorcinol, following which the process of the invention could be carried out. 6 e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C ) According to the present invention, a process for the preparation of compound of general formula I includes acetylating compound of general formula A. Following acetylation of compounds of general formula A, the acetylated material is reacted with hydrogen gas at pressures in the range of less than about 700 psig, preferably about 50 to about 600 psig, more preferably about 100 psig, in the presence of palladium catalyst, preferably, Palladium on Carbon catalyst. The catalyst is recyclable, preferably about five times. Palladium content is not greater than 10% by weight of the catalyst, preferably about 0.01 to about 10 % by weight of the substrate, more preferably about 5 % to about 10 % by weight of the substrate. The catalyst is used in the range of about 0.1 % to about 40 % by weight of compound of general formula A, preferably in the range of about 5 % to about 30 % by weight of compound of general formula A. Hydrogenation is carried out at a pH below 7.0, preferably in the presence of acetic acid, and at temperatures below 50 deg. C, preferably room temperature, for high yields. Following hydrogenation, the catalyst is removed (e.g., filtered), and the solution heated in the presence of water. Hydrolysis in is performed in acidic media, preferably aqueous acetic acid, at or above 23 °C, preferably about 23 °C to about 150 °C, more preferably about 100 °C. At the end of the reaction, the desired product may be purified by separation of the solvent using any known method of separation. The preferred method of separation of the desired products from the solvent is by filtration followed by distillation of the solvent, and re-crystallization. General synthetic procedures are as follows. e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C) I. Diacetylation of 4-Acylresorcinol General Procedure The 4-acylresorcinol A is dissolved in a mixture of acetic anhydride and triethylamine and the reaction is monitored using a suitable analytical method (i.e. TLC, GC, LC) until complete consumption of the starting material. The solvents are removed under reduced pressure and the product is purified using conventional methods (i.e. recrystallization, distillation, chromatography). II. Hydrogenation of 4-Acylresorcinol Diacetate General Procedure A high pressure reaction vessel is charged with a 4-acylresorcinol diacetate B in acetic acid and a catalyst is added (i.e. homogeneous or heterogeneous catalysts such as Pd attached to a suitable matrix). A catalyst is selected such that it is capable of being recycled at least five times. The reactor is pressurized with hydrogen (i.e. 100 to 800 psi) and stirred above 25 °C (i.e. 25 to 60 °C) until complete consumption of the reactant is observed as monitored using a suitable analytical method (i.e. TLC, GC, LC, hydrogen consumption). The reaction 8 e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C ) mixture is filtered through an insoluble support (i.e. celite, silica gel), the solvents removed under reduced pressure and the product purified using conventional methods (i.e. re-crystallization, distillation). The major product of hydrogenation is at least about 90 % mono-acetate and about 10 % di-acetate. III. Hydrolysis of 4-Acylresorcinol Mono-acetate acetic acid water heat General Procedure The 4-acylresorcinol monoacetate C (or di-acetate) is dissolved in aqueous acidic media (i.e. aqueous acetic acid) and stirred at or above 23 °C (i.e. 23 to 150 °C) until complete consumption of the reactant is observed as monitored using a suitable analytical method (i.e. TLC, GC, LC). The solvents are removed under reduced pressure and the product is purified using conventional methods (i.e. recrystallization, distillation, chromatography). The invention will now be illustrated with the help of the following non-limiting examples: EXAMPLES Methods and Materials: Gas Chromatoqraphy/mass spectroscopy (GC-MS): GC-MS was performed on a Finigen MAT mass spectrophotometer with A200S Autosampler Series Plus gas chromatrograph in conjunction with a GCQ 2.0 MS/MS Software. A DB-1 column ( 60 meter) was used. 9 e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C ) Gas Chromatography (GC): GC was performed on a Chemito 2000 Gas chromatographer (flame ionization) using a BP1 capillary column ( 30 meter x 0.25mm). The injection temperature was set at 250 C. Proton Magnetic Resonance (NMR): NMR spectra were recorded on a Bruker 200 MHZ instrument. Chemical shifts are reported in parts per million from tetramethanesilane as an internal standard. Spin multiplicities are indicated as follows: s ( singlet),d (doublet),t (triplet), m (multiplet) and br (broad). The deuterated NMR solvents contain 99.00-99.9% deuterium in the indicated position. All solvents were reagent grade and were used as received. All reagents were purchased from Aldrich or Sigma Chemical Companies and were used as received unless otherwise noted. The palladium on carbon catalyst is available from Englelhardt Corporation, Iselin, New Jersey. The examples below demonstrate that compounds of formula I can be prepared in high yield using the process as per the invention. EXAMPLE 1 Specific Diacetylation Procedure: 2,4-Dihydroxyacetophenone diacetate (B1) Triethyl-amine (142ml, 1.02mol) was added to a solution of 2,4-dihydroxyacetophenone (A1 or 2,4-DHAP) (70g, 0.46mol) in tetrahydrofuran 10 e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C) (700ml) at room temperature, followed by acetic anhydride (96ml, 1.02mol) and the solution stirred for 2.5 h. Additional triethylamine (40ml) and acetic anhydride (35ml) were added and the solution stirred for an additional 2 h. At this time, TLC [50uL aliquot into ethyl acetate:1 M HCI (500uL:500uL), ethyl acetate:hexane (1:1) eluent, UV and PMA stain visualization] showed the clean formation of a single product (Rf 0.42) and no starting material (Rf 0.49). The solvent was removed and the residue diluted with ethyl ether (300ml), washed successively with 1 M HCI (3 X 100ml) and saturated NaCI (1 X 100ml), dried (Na2SO4), filtered and the solvent removed to give a yellow orange-colored oil. Vacuum distillation of this material (collected between 125-130 °C @ 0.025mm Hg) gave pure product as a very pale light-yellow oil (99g, 91% yield, 98% purity by GC): 1H NMR (60 MHz, CDCI3) delta 2.30 (s, 3H), 2.34 (s, 3H), 2.54 (s, 3H), 7.07 (m, 2H), 7.86 (d, JJ = 8.6 Hz, 1H); m/z (El; M+) 236. Specific Hydrogenation Procedure: 4-Ethylresorcinol monoacetate (C1) A Parr hydrogenator (1 L) was charged with 2,4-dihydroxyacetophenone di-acetate (B1 or 2,4-DHAPDA) (1ml, 1.15g, 4.9mmol) and acetic acid (50 ml) under nitrogen. A suspension of 5% Pd/C (100mg, Engelhard) in acetic acid (50ml) was added and the reactor sealed, evacuated and purged with nitrogen (4X). The reactor was pressurized to 100 psi with hydrogen and stirred at 30 °C for 16 hr. At his time, GC showed the clean formation of product at the expense of starting material. The reactor was evacuated, purged with nitrogen and the mixture filtered through celite. The solvent was removed to give an amber-colored oil which crystallized upon overnight storage at 4 °C (746mg, 85%). The 11 e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C ) product was further purified by flash chromatography to give pure product as white needles: m.p. 40-41 °C; 1H NMR (60 MHz, CDCI3) 5 1.19 (t, JJ = 7.2 Hz, 3H), 2.36 (s, 3H), 2.57 (q, JJ = 7.3 Hz, 2H), 5.27 (s, 1H), 6.63 (m, 2H), 7.10 (d, JJ = 7.8 Hz, 1H); m/z (El; TMS derivatized; M+) 252. OX V -A 1 acetic acid (l^| water OH ^f^OX heat C1:X = Ac,H D1 Specific Hydrolysis Procedure: 4-Ethylresorcinol (D1) Crude 4-ethyl resorcinol monoacetate C1 (4-ERMA) (670mg) in acetic acid (100ml) was diluted with water (20ml) and the solution refluxed for 12 h. At this time, TLC [50uL aliquot into ethyl acetate:sat'd NaHC03 (500uL:500uL); 8% methanol:chloroform eluent, UV and PMA stain visualization] showed the clean formation of product (Rf 0.27) and traces of starting material (Rf 0.60). The solvent was removed under reduced pressure at EXAMPLE 2 This example demonstrates 4-ethyl resorcinol yields and purity at varying reaction conditions as shown in the Table below. The effects of temperature, pressure, solvent, nature of catalyst and pH on the catalytic hydrogenation of acetophenones (2,4-DHAP and 2,4-DHAPDA) were investigated. 12 e:\data\word\palents\Resorcinol\2-Completion4-8-05.doc J6912(C) TABLE 1. Hydrogenation of 2,4-Dihydroxyacetophenone (2,4-DHAP or A1) in Acetic Acid Entry 2.4-DHAP (M)a Cats. (Wqt %)b H2Press (psi) Temp. (°C) Rxn Time (hr)c 4-ER (%)d 2.4-DHAP (%)e By-products (Tr-%)f 1 0.13 10%Pd/C(10%) 300 25-30 15 57 0 13.68-18% 6.13-11% 6.22-11% 2 0.13 10%Pd/C(5%) 150 25-30 17 49 9 13.68-33% 6.13-4% 6.22-4% 3 0.13 10%Pd/C(5%) 40 25-30 17 41 26 13.68-27% 6.13-2% 6.22-2% 4 0.60 10%Pd/C(10%) 50 25-30 2 27 40 13.68-26% 6.13-1% 6.22-1% 6.95-3% 11.35-1% 5 0.13 10%Pd/C(5%) 40 25-30 114 26 5 13.68-45% 6.13-8% 6.22-8% 11.35-9% 6 0.13 10%Pd/C(5%)/HCI 150 25-30 17 2 98 7 0.13 10%Pd/C(5%)/ 150 25-30 17 0 0 8.78-9.01 TsOH (100%) 10.27-10.57 8 0.06 10%Pd/C(5%)/ 200 25-30 16 0 0 5.17-15% TsOH (1.4%) 6.13-20% 6.22-19% 8.43-25% a Molar concentration of 2,4-dihydroxyacetophenone (2,4-DHAP) in acetic acid. b Weight percent of catalyst and/or acid additive with respect to reactant (2,4-DHAP); Pd/C = palladium on carbon, TsOH = p-toluenesulfonic acid, HCI = hydrochloric acid. c Reaction time. d Percent of 4-ethylresorcinol (4-ER or D1) in the reaction mixture as determined by gas chromatography (i.e., GC yield). e Percent of unreacted 2,4-DHAP in the reaction mixture as determined by gas chromatography. f Percent and retention times (Tr) of by-products generated in the reaction mixture as determined by gas chromatography; — = no by-products generated. e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc 15 J6912(C) Hydrogenation of 2,4-Dihydroxyacetophenone Di-acetate (2,4-DHAPDA) TABLE 2. Effect of Solvent and Acidic Additives Entry 2.4-PHAPDA (M)a Cats. (Wgt %)b H2 Press (psi) Temp. (°C) Rxn Time (hr)c 4-ERMA/DA (%)d DHAPDA (%)e By-prod (Tr-%)' 1 0.04/Ac2O 10%Pd/C(10%) 200 25-30 16 0 100 2 0.04/AcOH 10%Pd/C(10%) 200 30-35 16 100/0 0 3 0.04/AcOH 10%Pd/C(10%)/ 200 25-30 16 90/10 0 TsOH (1.4%) TABLE 3. Effect of Catalyst Recyclability Entry 2.4-DHAPDA (M)a Cats. (Wqt %)" H, Press (psi) Temp. (°C) Rxn Time (hr)c 4-ERMA/DA (%)" DHAPPA (%)" Bv-prod (Tr-%)' 1 0.04/AcOH 5%Pd/C(10%) 100 25-30 16-18 95/5 0 2 0.04/AcOH 5%Pd/C( 3 0.04/AcOH 5%Pd/C( 4 0.04/AcOH 5%Pd/C( 5 0.04/AcOH 5%Pd/C( a Molar concentration of 2,4-dihydroxyacetophenome diacetate (2,4-DHAPDA) in acetic acid (AcOH) or acetic anhydride (Ac20). b Weight percent of catalyst and/or acid additive with respect to reactant (B1 or 2,4-DHAPDA); Pd/C = palladium on carbon, TsOH = p-toluenesulfonic acid. c Reaction time. d Percent of 4-ethylresorcinol monoacetate (4-ERMA or C1) / 4-ethylresorcinol diacetate (DA) in the reaction mixture as determined by gas chromatography. e Percent of unreacted 2,4-DHAPDA in the reaction mixture as determined by gas chromatography. f Percent and retention times (Tr) of by-products generated in the reaction mixture as determined by gas chromatography; = no by-products generated. e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc 16 J6912(C) Table 3 shows the effect of catalyst recyclability using 5 %Pd/C-Reduced (available from Engelhard, New Jersey) at optimal atmospheric conditions (i.e., no air exposure). Greater than about 90 % 4-ERMA is produced during this reaction step. 15 e:\data\word\patents\Resorcinol\2-Cornpletion4-8-05.doc J6912(C) WHAT IS CLAIMED IS: 1. A process for manufacturing compounds of general formula I: (I) comprising: I. Acetylation of compounds of general formula A: (A) To form acetylated product; II. Hydrogenation of the acetylated product to form hydrogenated product; III. Hydrolysis of the hydrogenated product to form said compound of general formula I; where R is hydrogen or an alkyl group having 1 to 18 carbon atoms, which is either straight chain, branched or cyclic, with or without hetero-atoms (oxygen, nitrogen or sulfur) anywhere in the chain or ring. 2. The process of claim 1, wherein said compound of general formula I is used for preparation of cosmetic compositions, particularly skin lightening cosmetic compositions. 16 e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc J6912(C) 3. The process of claim 1, wherein said Acetylation reaction is carried out at room temperature in presence of acetic anhydride. 4. The process of claim 1, wherein said Hydrogenation of said acetylated materials is carried by reaction with hydrogen gas at pressures in the range of less than about 700 psig, preferably about 50 to about 600 psig, more preferably about 100 psig, in the presence of palladium catalyst. 5. The process of claim 4, wherein said catalyst is Palladium on Carbon catalyst. 6. The process of claim 4, wherein said catalyst is capable of being recycled at least five times. 7. The process of claim 4, wherein said Hydrogenation reaction is carried out at a pH below 7.0. 8. The process of claim 4, wherein said Hydrogenation reaction is carried out at a temperature below 50 deg. C. 9. The process of claim 5, wherein said catalyst has a palladium content not greater than 10% by weight of the catalyst. 10. The process of claim 4, wherein said catalyst is used in the range of about 0.1 % to about 40 % by weight of compound of general formula A, preferably in the range of about 5 % to about 30 % by weight of compound of general formula A. 11. The process of claim 1, wherein said Hydrolysis reaction is in acidic media at or above 23 deg. C, preferably about 23 to about 150 deg. C. 12. The process of claim 11, wherein said acidic media comprise acetic acid. Dated this 24th day of May 2005 HINDUSTAN LEVER LTD e:\data\word\patents\Resorcinol\2-Completion4-8-05.doc (S. Venkatramani ) Sr Patents Manager J6912(C) Abstract The present invention relates to a process of manufacturing 4-alkyl resorcinol derivatives. More specifically, the present invention relates to a process of manufacturing 4-alkyl resorcinol derivatives by acetylation of 4-acyl resorcinol, followed by hydrogenation and hydrolysis.

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