Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K31/00—Medicinal preparations containing organic active ingredients
  • A61K31/33—Heterocyclic compounds
  • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
  • A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
  • A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
  • A61K31/4427—Non condensed pyridines; Hydrogenated derivatives thereof containing further heterocyclic ring systems
  • A61K31/4439—Non condensed pyridines; Hydrogenated derivatives thereof containing further heterocyclic ring systems containing a five-membered ring with nitrogen as a ring hetero atom, e.g. omeprazole
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• the present invention relates to novel acid addition salts of Dabigatran etexilate, processes for its preparation and a pharmaceutical composition containing the same,
• Form 1 generally named as Dabigatran etexilate, has the following chemical structure:
• Dabigatran etexilate is the oral pro-drug of the active moiety dabigatran (Formula 2) which is a univalent direct thrombin inhibitor that act as anticoagulants (delaying blood clotting) by directly inhibiting the enzyme thrombin.
• Dabigatran etexilate pro-drug was developed due to the limited oral availability of dabigatran.
• Dabigatran etexilate of Formula 1 is converted to actual effective compound namely dabigatran of Formula 2, in the body.
• the main category of indication for dabigatran etexilate of Formula 1 is the post operative prophylaxis of deep vein thrombosis and the prevention of strokes.
• Dabigatran and dabigatran etexilate were first disclosed in US Patent No. 6,087,380 ("the '380 patent").
• dabigatran etexilate of the Formula 1 is prepared by reacting l-memyl-2-p f-(4-amidino-pheny])-aminomethyl]-5-benzirnidazol- carbonate-N-(2-pyridyl)-[2-(ethoxy-carbonyl)-ethyl]-amide hydrochloride and hexyl- chloroformate.
• the thus-formed dabigatran etexilate is characterized by thin layer chromatography and mass spectrometry, however the '380 patent remain silent about the description relating to the crystallographic properties of the dabigatran etexilate base.
• Dabigatran etexilate is marketed in many countries as its methane sulfonate salt (Dabigatran etexilate mesylate) under the trade name PRADAXA® by Boehringer Ingelheim.
• the marketed dabigatran etexilate mesylate salt was disclosed in US Patent Application No. 2003/181488A1.
• PCT publication WO2005/028468 discloses three polymorphic forms of dabigatran etexilate mesylate.
• the polymorphic forms (Form I, II and hemihydrate) obtained from the base by crystallization are characterized by X-ray powder diffraction pattern and differential scanning calorimetry curves.
• US Patent Application No 2006/0247278 discloses various pharmaceutically acceptable salts of dabigatran etexilate namely hydrochloride, maleate, tartrate, salicylate, citrate, malonate salts and their hydrates thereof. These salts are characterized by differential scanning calorimetry curves.
• US Patent Application No 2010/0087488 discloses various salts of dabigatran etexilate and polymorphic forms thereof, wherein the salts are a) 2,5-dihydroxybenzoate, b) besylate, c) forms II, V and VI of the hydrochloride, d) cyclamate, e) edisylate, f) esylate, g) fumarate, h) D-glucuronate, i) glycolate, j) isethionate, k) L-malate, 1) D-malate, m) mandelate, n) naphthalene-l,5-disulfonate, o) naphthalene-2-sulfonate, p) oxalate, q) phosphate, r)
• PCT publication WO2011/110876 discloses salt forms of dabigatran etexilate such as phosphoric acid, fumaric acid, sulfuric acid (includes its monohydrate and dihydrate also), maleic acid, oxalic acid, hydrochloride salt (four forms), pTSA salt, mesylate salt form IV.
• PCT publication WO2012/044595 discloses crystalline dabigatran etexilate bismesylate, which intern prepared from dabigatran etexilate mesylate Form I in ethyl acetate.
• dabigatran etexilate mesylate provides good pharmaceutical activity
• Such * discoveries can also enlarge the repertoire of materials that a formulation scientist has available for designing for example a pharmaceutical dosage form of a drug with a targeted release profile or other desired characteristic.
• the pharmaceutically acceptable acid addition salts of dabigatran etexilate showing the same pharmacological activity as dabigatran etexilate mesylate may be used as active ingredients of anticoagulants. They may also serve as intermediates in manufacturing process of high pharmaceutical purity dabigatran etexilate.
• the present invention satisfies this need by providing pharmaceutically acceptable acid addition salts of dabigatran etexilate with enhanced solubility in water or aqueous media as an essential property of active pharmaceutical ingredients determining the performance of pharmaceutical formulation.
• the improved pharmaceutical property is selected from the group consisting of: increased solubility, increased dissolution, increased bioavailability, increased dose response, decreased hygroscopicity, decreased form diversity, more desired morphology, or other property described herein.
• the present invention provides novel acid addition salts of dabigatran etexilate of Formula 1 or its solvates or hydrates thereof;
• the acid addition salts are selected from the group comprising an anti-oxidative acids such as cinnamic acid and its derivatives selected from the group consisting of p- coumaric acid, Ferulic acid, Sinapic acid, Caffeic acid, Chlorogenic acid, Caftaric acid, Coutaric acid and the like; benzoic acid and its derivatives selected from the group consisting of p-hydroxy benzoic acid, Vanillic acid, Syringic acid, 4-(4-phenoxybenzoyl) benzoic acid, Gentisic acid, Protocatechuic acid, Gallic acid and the like; and other acids such as Quinic acid, Nitric acid, Lipoic acid and Aspartic acid.
• an anti-oxidative acids such as cinnamic acid and its derivatives selected from the group consisting of p- coumaric acid, Ferulic acid, Sinapic acid, Caffeic acid, Chlorogenic acid, Caftaric acid, Coutaric acid and the like
• benzoic acid and its derivatives selected
• the present invention provides novel acid addition salts of dabigatran etexilate, which exist in the form of polymorphs of salts, co-crystals, or polymorphs of co-crystals.
• the present invention provides a process for preparation of acid addition salts of dabigatran etexilate of Formula 1 or its solvates or hydrates thereof, comprising: a) providing a solution comprising dabigatran etexilate and acid addition salt in one or more solvents, and
• the acid addition salts are selected from the group comprising an anti-oxidative acids such as cinnamic acid and its derivatives selected from the group consisting of p- coumaric acid, Ferulic acid, Sinapic acid, Caffeic acid, Chlorogenic acid, Caftaric acid, Coutaric acid and the like; benzoic acid and its derivatives selected from the group consisting of p-hydroxy benzoic acid, Vanillic acid, Syringic acid, 4-(4-phenoxybenzoyl) benzoic acid, Gentisic acid, Protocatechuic acid, Gallic acid and the like; and other acids such as Quinic acid, Nitric acid, Lipoic acid and Aspartic acid.
• an anti-oxidative acids such as cinnamic acid and its derivatives selected from the group consisting of p- coumaric acid, Ferulic acid, Sinapic acid, Caffeic acid, Chlorogenic acid, Caftaric acid, Coutaric acid and the like
• benzoic acid and its derivatives selected
• the present invention provides a pharmaceutical composition comprising acid addition salts of dabigatran etexilate prepared by the processes of the present invention.
• Fig. 1 is the characteristic powder X-ray diffraction (XRD) pattern of crystalline dabigatran etexilate ferulate salt.
• Fig. 2 is the characteristic differential scanning calorimetric (DSC) thermogram of crystalline dabigatran etexilate ferulate salt.
• Fig. 3 is the characteristic powder X-ray diffraction (XRD) pattern of crystalline dabigatran etexilate caffate salt.
• Fig. 4 is the characteristic differential scanning calorimetric (DSC) thermogram of crystalline dabigatran caffate salt.
• Fig. 5 is the characteristic powder X-ray diffraction (XRD) pattern of crystalline dabigatran etexilate gallate salt.
• Fig. 6 is the characteristic differential scanning calorimetric (DSC) thermogram of crystalline dabigatran etexilate gallate salt.
• Fig. 7 is the characteristic powder X-ray diffraction (XRD) pattern of crystalline dabigatran etexilate nitrate salt.
• Fig. 8 is the characteristic differential scanning calorimetric (DSC) thermogram of crystalline dabigatran etexilate nitrate salt.
• the present invention addresses a need in the art by providing new acid addition salts of dabigatran etexilate, or its solvates or hydrates thereof.
• the present inventors have identified new acid addition salts of dabigatran etexilate, or its solvates or hydrates thereof. These salt forms may be in the form of solvates, hydrates, polymorphs of salts, co-crystals, or polymorphs of co-crystals.
• the present invention provides novel acid addition salts of dabigatran etexilate of Formula 1 or its solvates or hydrates thereof;
• the acid addition salts are selected from the group comprising an anti-oxidative acids such as cinnamic acid and its derivatives selected from the group consisting of p- coumaric acid, Ferulic acid, Sinapic acid, Caffeic acid, Chlorogenic acid, Caftaric acid, Coutaric acid and the like; benzoic acid and its derivatives selected from the group consisting of p-hydroxy benzoic acid, Vanillic acid, Syringic acid, 4-(4-phenoxybenzoyl) benzoic acid, Gentisic acid, Protocatechuic acid, Gallic acid and the like; and other acids such as Quinic acid, Nitric acid, Lipoic acid and Aspartic acid.
• an anti-oxidative acids such as cinnamic acid and its derivatives selected from the group consisting of p- coumaric acid, Ferulic acid, Sinapic acid, Caffeic acid, Chlorogenic acid, Caftaric acid, Coutaric acid and the like
• benzoic acid and its derivatives selected
• the present invention provides novel acid addition salts of dabigatran etexilate, in particular anti-oxidant acid addition salts of dabigatran etexilate or hydrates or solvates thereof; wherein the anti-oxidative acids are selected from the group comprising cinnamic acid and its derivatives selected from the group consisting of p- coumaric acid, Ferulic acid, Sinapic acid, Caffeic acid, Chlorogenic acid, Caftaric acid, Coutaric acid and the like; benzoic acid and its derivatives selected from the group consisting of p-hydroxy benzoic acid, Vanillic acid, Syringic acid, 4-(4-phenoxybenzoyl) benzoic acid, Gentisic acid, Protocatechuic acid, Gallic acid and the like.
• the anti-oxidative acids are selected from the group comprising cinnamic acid and its derivatives selected from the group consisting of p- coumaric acid, Ferulic acid, Sinapic acid, Caffeic acid, Chlor
• the anti-oxidant acids used in the present invention are not only intended for formation of pharmaceutically acceptable salt forms of dabigatran, etexilate, the obtained salts of dabigatran etexilate itself can advantageously be useful for therapeutical use, for example, anti-oxidant acids can stabilize the body's metabolism by defending against damage caused by free radicals.
• the anti-oxidant acid salts of dabigatran etexilate are more effective with respect to therapeutic activity of the dabigatran etexilate as compared to the dabigatran etexilate salt form with non anti-oxidant acids described in the afore mentioned literature.
• the present invention provides dabigatran etexilate ferulate salt or its solvates or hydrates thereof.
• the present invention provides dabigatran etexilate ferulate salt in crystalline form.
• the present invention provides crystalline dabigatran etexilate ferulate salt characterized by an X-Ray diffraction (XRD) pattern substantially in accordance with Fig. 1.
• XRD X-Ray diffraction
• the present invention provides crystalline dabigatran etexilate ferulate salt characterized by differential scanning calorimetric (DSC) thermogram substantially in accordance with Fig. 2.
• DSC differential scanning calorimetric
• the present invention provides dabigatran etexilate caffate salt or its solvates or hydrates thereof.
• the present invention provides dabigatran etexilate caffate salt in crystalline form.
• the present invention provides crystalline dabigatran etexilate caffate salt characterized by an X-Ray diffraction (XRD) pattern substantially in accordance with Fig. 3.
• XRD X-Ray diffraction
• the present invention provides crystalline dabigatran etexilate caffate salt characterized by differential scanning calorimetric (DSC) thermogram substantially in accordance with Fig. 4.
• DSC differential scanning calorimetric
• the present invention provides dabigatran etexilate gallate salt or its solvates or hydrates thereof.
• the present invention provides dabigatran etexilate gallate salt in crystalline form. In another embodiment, the present invention provides crystalline dabigatran etexilate gallate salt characterized by an X-Ray diffraction (XRD) pattern substantially in accordance with Fig. 5.
• XRD X-Ray diffraction
• the present invention provides crystalline dabigatran etexilate gallate salt characterized by differential scanning calorimetric (DSC) thermogram substantially in accordance with Fig. 6.
• DSC differential scanning calorimetric
• the present invention provides novel acid addition salts of dabigatran etexilate, wherein the acid addition salts of dabigatran etexilate are selected from dabigatran etexilate cinnamic acid salt, dabigatran etexilate sinapic acid salt, dabigatran etexilate p-coumaric acid salt, dabigatran etexilate chlorogenic acid salt, dabigatran etexilate caftaric acid salt, dabigatran etexilate coutaric acid salt, dabigatran etexilate benzoic acid salt, dabigatran etexilate p-hydroxy benzoic acid salt, dabigatran etexilate vanillic acid salt, dabigatran etexilate syringic acid salt, dabigatran etexilate 4-(4- phenoxybenzoyl) benzoic acid salt, dabigatran etexilate gentisic acid salt and dabigatran
• the present invention provides novel acid addition salts of dabigatran etexilate, in particular acid addition salt selected from the group comprising Quinic acid, Nitric acid, Lipoic acid and Aspartic acid.
• the present invention provides dabigatran etexilate quinate salt or its solvates or hydrates thereof.
• the present invention provides dabigatran etexilate nitrate salt or its solvates or hydrates thereof.
• the present invention provides dabigatran etexilate nitrate salt in crystalline form.
• the present invention provides crystalline dabigatran etexilate nitrate salt characterized by an X-Ray diffraction (XRD) pattern substantially in accordance with Fig. 7.
• XRD X-Ray diffraction
• the present invention provides crystalline dabigatran etexilate nitrate salt characterized by differential scanning calorimetric (DSC) thermogram substantially in accordance with Fig. 8.
• DSC differential scanning calorimetric
• the present invention provides dabigatran etexilate lipoate salt or its solvates or hydrates thereof.
• the present invention provides dabigatran etexilate aspartate salt or its solvates or hydrates thereof.
• the present invention provides characterization of acid addition salts of dabigatran etexilate of the present invention characterized by X-ray powder diffraction (XRD) pattern and/or melting point.
• XRD X-ray powder diffraction
• the present invention provides a process for preparation of acid addition salts of dabigatran etexilate of Formula 1 or its solvates or hydrates thereof, comprising:
• the acid addition salts are selected from the group comprising an anti-oxidative acids such as cinnamic acid and its derivatives selected from the group consisting of p- coumaric acid, Ferulic acid, Sinapic acid, Caffeic acid, Chlorogenic acid, Caftaric acid, Coutaric acid and the like; benzoic acid and its derivatives selected from the group consisting of p-hydroxy benzoic acid, Vanillic acid, Syringic acid, 4-(4-phenoxybenzoyl) benzoic acid, Gentisic acid, Protocatechuic acid, Gallic acid and the like; and other acids such as Quinic acid, Nitric acid, Lipoic acid and Aspartic acid.
• an anti-oxidative acids such as cinnamic acid and its derivatives selected from the group consisting of p- coumaric acid, Ferulic acid, Sinapic acid, Caffeic acid, Chlorogenic acid, Caftaric acid, Coutaric acid and the like
• benzoic acid and its derivatives selected
• the acid addition salts are selected from the group consisting of Ferulic acid, Caffeic acid, Gallic acid and Nitric acid.
• the starting dabigatran etexilate, used in the present invention can be prepared by any known method for example dabigatran etexilate may be synthesized as disclosed in U.S. Patent No. 6,087,380.
• the dabigatran etexilate in the step a) may be any crystalline or other form of dabigatran etexilate, including various solvates, hydrates or dabigatran etexilate obtaining as existing solution from a previous processing step.
• the one or more solvent include, but are not limited to water, lower alcohols, ketones, esters, ethers, C5-C7 linear, branched or cyclic, saturated or unsaturated hydrocarbons, nitriles, halogenated hydrocarbons, or mixtures thereof.
• the suitable organic solvent includes, but are not limited to methanol, ethanol, isopropanol, acetone, methylethylketone, methyl iso butyl ketone, methyl acetate, ethyl acetate, isopropyl acetate, tetrahydrofuran (THF), isopropyl ether (IPE), ter-butyl methyl ether, acetonitrile, propionitrile, methylene chloride, chloroform, toluene, cyclohexane, hexane, heptanes and the like and the mixtures thereof.
• the solution comprising dabigatran etexilate free base and acid addition salt of step a) can be provided by mixing the solution of dabigatran etexilate free base with acid addition salt.
• solution of dabigatran etexilate free base intern can be provided by dissolving dabigatran etexilate free base in suitable organic solvent.
• acid addition salts may be added to the solution of dabigatran etexilate either in natural state or in solution.
• solution of acid addition salt can be prepared by dissolving the acid addition salt in a suitable solvent.
• the temperature suitable for providing a solution comprising dabigatran etexilate and acid addition salt in one or more solvents is from ambient temperature to about boiling point of the solvent; preferably at a temperature of about 30°C to about 90°C.
• the isolation of the dabigatran etexilate acid addition salt can be induced by reducing the temperature of reaction mixture, especially if initial temperature of reaction mixture is elevated.
• the isolation can also be induced by reduction of solution volume, preferably under reduced pressure, spray drying, freeze drying, agitated thin film evaporator (ATFE), by complete evaporation of solvent or crystallization.
• the isolation may be caused by adding an antisolvent to the reaction solution to precipitation.
• the isolated acid addition salt of dabigatran etexilate can optionally be washed with one or more organic solvents, and finally resulted pure dabigatran etexilate may be recovered by any conventional methods such as filtering.
• the suitable organic solvent used include any suitable solvent as described herein; preferably the suitable organic solvent is selected from the group consisting of methanol, ethanol, acetone, THF, acetonitrile, ethyl acetate, IPE and mixtures thereof.
• the resulted pure dabigatran etexilate may be recovered by any conventional methods such as filtration, solvent precipitation, spray drying, freeze drying, agitated thin film evaporator (ATFE) and the like.
• the present invention provides a process for preparing acid addition salts of dabigatran etexilate, wherein the acid addition salt is ferulic acid, comprising a) providing a solution of dabigatran etexilate and ferulic acid in one or more solvents and b) isolating the dabigatran etexilate ferulate salt.
• the suitable solvent used is selected from the group consisting of methanol, ethanol, acetone, THF, acetonitrile, ethyl acetate, IPE and mixtures thereof, preferably acetone.
• the solution may be formed by heating the mixture at a temperature of about 30°C to about reflux temperature, preferably about 40°C to about 75°C.
• the dabigatran ferulate salt can be isolated by any known techniques such as cooling the solution to precipitation, crystallization, solvent precipitation, spray drying, freeze drying, agitated thin film evaporator (ATFE) and the like.
• Dabigatran etexilate ferulate salt prepared according to such procedure exhibits a powder X-ray diffraction pattern substantially in accordance with Figure. 01.
• the present invention provides a process for preparing acid addition salt of dabigatran etexilate, wherein acid addition salt is caffeic acid comprising a) providing a solution of dabigatran etexilate and caffeic acid in one or more solvents and b) isolating the dabigatran etexilate caffate salt.
• the suitable solvent used is selected from the group consisting of methanol, ethanol, acetone, THF, acetonitrile, ethyl acetate, IPE and mixtures thereof; preferably acetone.
• the solution may be formed by heating the mixture at a temperature of about 30°C to about reflux temperature, preferably about 40°C to about 75°C.
• the dabigatran caffate salt can be isolated by any known techniques such as cooling the solution to precipitation, crystallization, solvent precipitation, spray drying, freeze drying, agitated thin film evaporator (ATFE) and the like.
• Dabigatran etexilate caffate salt prepared according to such procedure exhibits a powder X-ray diffraction pattern substantially in accordance with Figure. 03.
• the present invention provides a process for preparing acid addition salt of dabigatran etexilate, wherein acid addition salt is gallic acid comprising a) providing a solution of dabigatran etexilate and gallic acid in one or more solvents and b) isolating the dabigatran etexilate gallate salt.
• the suitable solvent used is selected from the group consisting of methanol, ethanol, acetone, THF, acetonitrile, ethyl acetate, IPE and mixtures thereof; preferably acetone.
• the solution may be formed by heating the mixture at a temperature of about 30°C to about reflux temperature, preferably about 40°C to about 75°C.
• the dabigatran gallate salt can be isolated by any known techniques such as cooling the solution to precipitation, crystallization, solvent precipitation, spray drying, freeze drying, agitated thin film evaporator (ATFE) and the like.
• Dabigatran etexilate gallate salt prepared according to such procedure exhibits a powder X-ray diffraction pattern substantially in accordance with Figure. 05.
• the present invention provides a process for preparing acid addition salt of dabigatran etexilate, wherein acid addition salt is nitric acid comprising a) providing a solution of dabigatran etexilate and nitric acid in one or more solvents and b) isolating the dabigatran etexilate nitrate salt.
• the suitable solvent used is selected from the group consisting of methanol, ethanol, acetone, THF, acetonitrile, ethyl acetate, IPE and mixtures thereof; preferably acetone.
• the solution may be formed by heating the mixture at a temperature of about 30°C to about reflux temperature, preferably about 40°C to about 75 °C.
• the dabigatran nitrate salt can be isolated by any known techniques such as cooling the solution to precipitation, crystallization, solvent precipitation, spray drying, freeze drying, agitated thin film evaporator (ATFE) and the like.
• Dabigatran etexilate nitrate salt prepared according to such procedure exhibits a powder X-ray diffraction pattern substantially in accordance with Figure. 07.
• the present invention provides novel acid addition salts of dabigatran etexilate, having a chemical purity of 96% or more as measured by HPLC, preferably 99% or more, more preferably 99.5% or more.
• novel acid addition salts of dabigatran etexilate of the present invention can be used as intermediate or as starting material for the preparation of other pharmaceutically acceptable acid salts of dabigatran etexilate, for example dabigatran etexilate mesylate.
• the present invention provides a pharmaceutical composition
• a pharmaceutical composition comprising a therapeutically effective amount of acid addition salts of dabigatran etexilate of the invention, preferably dabigatran etexilate ferulate salt, dabigatran etexilate caffate salt, dabigatran etexilate gallate salt or dabigatran etexilate nitrate salt with at least one pharmaceutically acceptable carrier or other excipients.
• the pharmaceutical composition can be useful for post operative prophylaxis of deep vein thrombosis and the prevention of strokes.
• Pharmaceutical acceptable salts in accordance with present invention can be embodied for example in form of tablet, capsules, pellets, granules and suppositories or their combined forms.
• Pharmaceutical composition in accordance with present invention can be suitable for immediate release or modified release of dabigatran etexilate ' salts of the present invention.
• Solid pharmaceutical compositions can be for example coated with aim of increasing peletibility or regulating the dis

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Pharmacology & Pharmacy (AREA)
• Epidemiology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=52629059

Family Applications (1)

Country Status (2)

Family Cites Families (4)

• 2014
  • 2014-09-03 WO PCT/IN2014/000575 patent/WO2015033353A2/en not_active Ceased
  • 2014-09-03 IN IN3939CH2013 patent/IN2013CH03939A/en unknown

Also Published As

Similar Documents

Legal Events