Title of Invention

A PROCESS FOR THE PREPERATION OF PHOTOSTABILIZER

Abstract The present invention relates to a novel photo-stabilizer of general formula (I), wherein RI is hydrogen, halogen, C1to C12 alkyl, alkoxy (linear and branched), Rais halogen, C1 to C5alkyl, cyclopentyl, cyclohexyl or cumyl, RI is hydrogen, C1 to R4 alkyl, R4 is methyl or ethyl, R5is C1 - C8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl, X is O, NH, C1 - C8 alkoxy and alkylamino (linear or branched).
Full Text This invention relates to a process for the preparation of a novel photo-stabilizer having general formula (I):
(Formula Removed)
wherein:
R1 is hydrogen, halogen, C1 to C12: alkyl, alkoxy (all linear and branched), R2 is hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl, R3 is hydrogen, C1-C4 alkyl R4 is methyl, ethyl, R5 C1-C8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl X is O, NH,C1-C8 alkyloxy and alkylamino: (linear or branched) and the process for the synthesis thereof. More particularly it relates to the said compound and its preparation, using compound having formula (II)
(Formula Removed)
(II) wherein: R1 is hydrogen, halogen,C1 to C12 : alkyl, alkoxy (all linear and branched), R2 is
hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl with compound having
formula (IV).
(Formula Removed)

wherein:
R3 is hydrogen, C1-C4 alkyl, R4 is methyl, ethyl, R5 C1-C8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl, X is OH, NH2, C1-C8 alkyloxy and alkylamino: (linear or branched)
Polymers have replaced metals, glass, ceramics and papers in packaging, automobiles, building construction, electronics, electrical equipment, furniture, pipes and heavy industrial equipments. In a nutshell, from agriculture to transport and aerospace to food packaging, the use of plastics has become an integral part of our daily life. Polymers, all natural and synthetic, in common use, are susceptible to thermal/ photo-oxidative degradation upon exposure to natural and artificial weathering. The deterioration of these polymeric materials is mainly due to the UV portion of sunlight reaching the earth surface. The net result of degradation is the loss in the molecular weight and macroscopic physical properties. In order to avoid this loss different types of photo-stabilizers have been devised that protect the polymeric substrate from detrimental effect of light. The compatible and mobile light stabilizers usually prove to be the best choice to attain the desired photostability. Most of these stabilizers are commercially available and are successfully employed, single and/or in combination with other stabilizers for the polymer stabilization. Researchers have even attempted to study the combined effect of screeners, quenchers, ultraviolet absorbers and thermal stabilizers. An ample literature on the synthesis and application of these photostabilizers is available to date. Depending upon the type of combination, the effect of the stabilizers can be synergistic and antagonistic. The efficacy of the stabilizer depends on many factors viz. type of combination, proportion of additive, compatibility with the polymer and molecular weight of the stabilizer. Hindered amine light stabilizer (HALS) and benzotriazole based UV absorbers are known to

work in synergism and there is no literature on the synthesis of the coupled derivatives of HALS and UV absorbers. Keeping in view, all the above-mentioned requirements we have designed and synthesized a novel HALS coupled to an UV absorber. Following patents and literature provide information about synthesis of the photo-stabilizers and the photo-stabilization efficiencies of HALS and UV absorbers solely in presence of each other. JP 2000119260: April 2000, US 5977219 A2: November 1999, JP 4263874 A2 September 1999, EP 924248 Al: June 1999, US 5739348 A: April 1998, W0 9739052 Al: October 1997, US 5362881 A November 1994, US 5086097 A4 February 1994, Polym. Photochem., 5, 351 (1984), Polym. Degrad. Stab., 8, 133 (1984) and Polym. Degrad. Stab.32,71 (1991). The process for the synthesis of compound having formula (II) has been disclosed in our co-pending patent No. (Foreign Appl. 09/749,277). Moreover, an online search using SCIFINDER and CHEMICAL ABSTRACT search engines didn't reveal any molecule similar to that, we have claimed over here.
The objective of the present invention is therefore, to provide a process for the preparation of novel Tinuvin P-Hindered Amine Light Stabilizer (TP-HALS) derivatives, which can fulfill the above-mentioned prerequisites. Moreover, this class of combination of HALS and benzotriazole are known to be compatible with polyolefins, polycarbonate, polystyrene and diene-elastomers and can even be added in an additive proportion to obtain desired photo-stability of various other polymers. The present invention provides novel TP-HALS derivatives having general formula
(Formula Removed)

wherein:
R1 is hydrogen, halogen,C1-C12 : alkyl, alkoxy (all linear and branched), R2 is
hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl, R3 is hydrogen, C1-C4 alkyl
R4 is methyl, ethyl, R5 isC1-C8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and
allyl, X is O, NH, C1-C8 alkyloxy and alkylamino: (linear or branched) and the
process for the synthesis thereof.
Accordingly present invention "A PROCESS FOR THE PREPARATION OF
NOVEL PHOTO-STABILIZER: HALS COUPLED TO AN UV ABSORBER"
which comprises of dissolving a compound having formula (II) (which is described in
our co-pending patent application no. (Foreign Appl. 09/749,277)

(Formula Removed)
wherein:
R1 is hydrogen, halogen,C1 to C12 : alkyl, alkoxy (all linear and branched), R2 is
hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl, along with an organic base
in a round bottom flask (RB) containing a dry organic solvent under strictly inert
condition, agitating it initially for a period of 20-30 minutes followed by addition of
an hydroxy 1 protecting group and stirring the reaction mixture for 10-14 hrs under
inert atmosphere, followed by evaporating the organic solvent and drying the contents
of the RB and consequently dissolving it in a low boiling organic solvent followed by
filtration of the insoluble mass of the RB and evaporating the solvent to give a
compound having general formula (III)
(Formula Removed)

wherein:
R1 is hydrogen, halogen,C1 to C12 : alkyl, alkoxy (all linear and branched), R2 is
hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl and Y is
tertbutyldimethylsilyl, tert-butyl-di-phenylsilyl, dimethylthexylsilyl, benzoyl, benzyl,
and acetyl.
Dissolving the compound having formula (III) in an RB containing a dry organic
solvent under inert condition and simultaneously dissolving compound having
formula (IV)
(Formula Removed)
wherein:
R3 is hydrogen, C1-C4 alkyl, R4 is methyl, ethyl, R5 C1-C8 alkyl, alkyl phenyl,
alkoxy, acyl, cycloalkyl and allyl, X is OH, NH2, C1-C8 alkyloxy and alkylamino:
(linear or branched) in a separate RB in the same solvent and adding to it a dry metal
hydride, agitating the contents of the flask for 30-60 mins, cooling it to 4-8 °C and
then adding to it the contents of the first RB gradually over a period of 30-60
minutes, agitating the reaction mixture for 2-4 hrs, followed by refluxing the same for
2-4 hrs cooling the reaction mixture to room temperature and agitating for 4-6 hrs

followed by evaporating the organic solvent under reduced pressure, dissolving the solid mass in water and extracting the product in an organic solvent through repeated extractions and evaporating the organic solvent leads to a compound having formula (V)

(Formula Removed)
wherein:
R1 is hydrogen, halogen, C1 to C12 : alkyl, alkoxy (all linear and branched), R2 is
hydrogen,C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl, R3 is hydrogen, C1-C4 alkyl
R4 is methyl, ethyl, R5 C1-C8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl,
X is O, NH, C1-C8 alkyloxy and alkylamino: (linear or branched) and Y is tert-
butyldimethylsilyl, tert-butyl-di-phenylsilyl, dimethylthexylsilyl, benzoyl, benzyl, and
acetyl.
Taking the compound (V) in an RB with a hydroxy deprotecting reagent and stirring
the reaction mixture at room temperature for 1-3 hrs followed by addition of water
and extracting the product in an organic solvent, drying the solvent with an anhydrous
inorganic salt after neutralization with an inorganic base and evaporating the solvent
gives the compound having formula (I).
(Formula Removed)
Wherein:
R1 is hydrogen, halogen, C1to C12 : alkyl, alkoxy (all linear and branched), R2 is
hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl, R3 is hydrogen, C1-C4 alkyl
R4 is methyl, ethyl, R5 C1-C8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl
X is O, NH, C1-C8 alkyloxy and alkylamino: (linear or branched).
In one of the embodiments of the present invention, the organic solvent used for
dissolving the compound having formula (II) is selected from, pyridine,
dichloromethane, dimethylformamide, tetrahydrofuran, acetonitrile, and 1,4-dioxane .
In one of the other embodiments of the present invention, the base used to react with
compound having formula (II) is selected from imidazole, pyridine, 2,6-lutidine,
trimethyl amine, mercaptobenzoxazole and alkyl substituted pyridine.
In yet another embodiment the hydroxy protecting group is selected from, tert-
butyldimethylsilyl chloride, tert-butyl-di-phenylsilyl chloride, dimethylthexylsilyl
chloride, acetyl chloride, benzoyl chloride, benzyl bromide, benzoic acid, acetic
anyhydride and acetic acid.
In an another embodiment the catalyst used is selected from dimethyl aminopyridine,
diethyl aminopyridine, dimethyl aniline, dicyclohexyl carbodimide and hydroxy
benzotriazole.
In yet another embodiments of the present invention, the organic solvent used for
dissolving the crude mass is selected from dichloromethane, chloroform, acetone,
diethyl ether and benzene.
In an embodiment the solvent used to dissolve the compound (III) is selected from
dimethylformamide, tetrahydrofuran, acetonitrile, 1,4-dioxane and dichloromethane.
In another embodiment the hindered amine having general formula (IV) added to
react with compound (III) is selected from 1,2,2,6,6- pentamethyl-4-aminopiperidine,

l,2,2,6,6-pentamethyl-4-piperidinol, l,2,2,4,6,6-hexamethyl-4-aminopiperidine,
1,2,2,6,6- pentamethyl-4-ethylaminopiperidine and its derivatives as mentioned above.
In yet another embodiment the metal hydride is selected from sodium hydride and
potassium hydride.
In yet another embodiment the solvent used for extracting the product from the aqueous
medium is selected from dichloromethane, dichloroethane, ethyl acetate, diethyl ether,
benzene and n-hexane.
In yet another embodiment hydroxy deprotecting agent for deprotecting the compound
(V) is selected from, tetrabutyl ammonium fluoride, boron triflouride, boron trichloride,
boron tribromide, aluminum chloride, sodium bicarbonate, aqueous ammonia,
hydrochloric acid, lithium chloride and lithium aluminum hydride.
In yet another embodiment the solvent used for extracting the product from the aqueous
medium is selected from dichloromethane, dichloroethane, ethyl acetate, diethyl ether,
benzene and n-hexane.
In yet another embodiment the inert gas is selected from Nitrogen and Argon.
In yet another embodiment the inorganic base used to neutralize the solvent fraction
containing the product is selected from sodium carbonate, sodium bicarbonate,
potassium bicarbonate and potassium carbonate.
HALS monomers and some of its derivatives may be prepared by any of the methods
known in the art including those disclosed in Patents No. JP 53015385 28 (July 1978),
Swiss CH 610898 (15 May 1979), Swiss CH 605927 (Oct 1978), Brit. GB 1492494
(Nov 1977) and Literature: T. Tsuchiya and H. Sashida, Heterocycles, 14, 1925-8
(1980). HALS namely 2,2,6,6-tetramethyl piperidine and 2,2,6,6-tetramethyl-4-
piperidinol may be prepared by synthetic route disclosed by W. B. Lutz, S. Lazams
and R. I. Meltzer, J. Org. Chem., 14, 530 (1949) where as the hydroxy benzotriazoles

can be prepared by any of the above mentioned methods, disclosed in the patents and literature. All these patents and literature are incorporated herein by reference. The process of the present invention is described herein below with references to examples which are illustrative only and should not be construed to limit the scope of the present invention in any manner whatsoever.
Example 1
Synthesis of 2-(2'-tert-butyldimetylsilyIoxy-5'-bromomethylphenyl) benzotriazole
This compound was synthesized strictly under dry and inert reaction conditions. In a 100 mL capacity RB, 2-(2'-hydroxy-5'-bromomethyl phenyl) benzotriazole (3.0 gms, 0.00986M) was taken along with imidazole (2.1 gm, 0.0295 M) and applied an inert atmosphere using Argon gas. Added 10 ml of dry pyridine and agitated the reaction mixture for 20-60 min. The reaction mixture becomes very thick and difficult to stir. To this mixture, tert-butyl dimethyl silyl chloride (5.2 g, 0.0345 M) was added under inert condition and continued agitating the reaction mixture for 10-14 hrs. After checking the TLC for the completion of the reaction, the pyridine from the RB was evaporated to dryness under vacuum. The contents of the RB were consequently dissolved in 15 mL dichloromethane. The insoluble mass was filtered off and the mother liquor was evaporated under vacuum to give (a semi crystalline rust colored compound) 2-(2'-tert-butyl-di-metylsilyloxy-5'-bromomethylphenyl)benzotriazole. The crude product weighed 3.30 gms to give 80 % yield. The crude compound was purified using column chromatography employing a suitable solvent system. The yield of the pure compound was 76 % and its m.p. = 162-164° C.

Example 2 Synthesis of 2-[2'-tert-butyldimetylsilyloxy-5'-methyIeneoxy(( 1", 2", 2", 6", 6"-pentamethyl —4"- piperidinyl) phenyl )benzotriazole
This compound was synthesized strictly under dry and inert reaction conditions. The compound 2-(2'-tert-butyl-di-metylsilyloxy-5'-bromomethylphenyl)benzotriazole (2.1 gms, 0.00501 M) was taken in one 25 mL capacity RB and dissolved in 8 mL dry dimethylformamide (DMF) under Argon atmosphere with stirring. In an another two necked RB, l,2,2,6,6-pentamethyl-4-piperidinol (1.0356 gm, 0.00601 M) and sodium hydride (0.3 gms, 0.01252 M) were taken and dissolved in 6 mL dry DMF with stirring under Argon atmosphere. This reaction mixture was agitated for almost 60 min and then cooled to 4-8 °C. To this reaction mixture added the contents of the first RB gradually over a period of 30-60 min. This reaction mixture was further agitated for 2-4 hrs followed by refluxing the same for a period of 2-4 hrs. The contents of the RB were cooled to room temperature and further agitated for 4-6 hrs at room temperature. The solvent in the RB was evaporated under reduced pressure and the solid mass in the RB was dissolved in 15 mL water and repeatedly extracted with dichloromethane (4x10 mL). Dichloromethane was then evaporated under vacuum at 38 °C over a rotavapor to give pale yellow colored crystalline product 2-[2'-tert-butyldimetylsilyloxy-5'-methyleneoxy((l", 2", 2", 6", 6"-pentamethyl4"-piperidinyl) phenyl )benzotriazole. The TLC showed very little amount of unreacted starting material. The crude yield was 2.22gms (87%). The product was purified by rectystalization technique using an appropriate organic solvent to get (83 %) yield of pure product.

Example 3 Synthesis of 2-[2'-hydroxy-5'-methyleneoxy(( 1", 2", 2", 6", 6"-pentamethyl -4"-piperidinyl) phenyl )benzotriazole
The compound 2-[2'-tert-butyldimetylsilyloxy-5'-methyleneoxy(( 1", 2", 2", 6", 6"-pentamethyl—4"- piperidinyl) phenyl )benzotriazole (2.0 g, 0.003937 M) was taken in an RB with a tetrabutyl ammonium fluoride [ 4.71 mL, 0.004724 M (1.0 M solution in THF)] and agitated the reaction mixture at room temperature for 1-3 hrs under anhydrous conditions, followed by addition of 10 mL water and extracting the product in DCM (4x10 mL). The solvent was dried with anhydrous magnesium sulfate after neutralization with anhydrous potassium carbonate. Evaporating the solvent gave the product 2-[2'-tert-butyldimetylsilyloxy-5'-methyleneoxy (( 1", 2", 2", 6", 6"-penta methyl -4"-piperidinyl) phenyl )benzotriazole with a crude yield of 1.39 gms. (90 %). The process of the present invention has four distinct merits:
1) The process is an economic.
2) The process comprises of commonly available organic reagents and mild reaction conditions.
3) High yield (> 75 %) can be achieved very easily.
4) Reaction can be carried out via very facile route with very simple and moderate reaction conditions.




We claim:
l.A Tinuvin P-Hindred Amine Light Stabilizer of the general formula (I) wherein:R1 is hydrogen, halogen, C1 to C12: alkyl, alkoxy (all linear and branched), R2 is hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexy] or cumyl, R3 is hydrogen, C1-C4 alkyl R4 is methyl or ethyl, R5 C1 - C8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl X is O, NH, Ci-Cg alkyloxy and alkylamino: (linear or branched) and derivatives thereof.

(Formula Removed)
2. A Process for the preparation of the Tinuvin P-Hindred Amine Light Stabilizer as claimed in claim 1 of the general formula (I)
(Formula Removed)

wherein:
R1is hydrogen, halogen, C1 to C12: alkyl, alkoxy (all linear and branched), R2 is hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl, R3 is hydrogen, C1-C4 alkyl R4 is methyl, ethyl, R5 C1-C8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl X is O, NH, C1-C8 alkyloxy and alkylamino: (linear or branched) which comprises of dissolving a compound having formula (II),
(Formula Removed)

where in:
R1 is hydrogen, halogen,C1 to C12 : alkyl, alkoxy (all linear and branched), R2 is
hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl, along with an organic
base and a catalyst in a round bottom flask (RB) containing a dry organic solvent
under strictly inert condition, agitating it initially for a period of 20-30 minutes,
followed by the addition of an hydroxy protecting group and stirring the reaction
mixture for 10-14 hrs under inert atmosphere followed by evaporating the organic
solvent and drying the contents of the RB and consequently dissolving it in a low
boiling organic solvent followed by filtration of the insoluble mass of the RB and
evaporating the solvent to give a compound having general formula (III),
(Formula Removed)
wherein:
R1 is hydrogen, halogen,C1 to C12 : alkyl, alkoxy (all linear and branched), R2 is
hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl and Y is
tertbutyldimethylsilyl, tert-butyl-di-phenylsilyl, dimethylthexylsilyl, benzoyl,
benzyl, and acetyl, dissolving the compound having formula (III) in an RB
containing a dry organic solvent under inert condition and simultaneously
dissolving compound having formula (IVU„
(Formula Removed)
where in:
R3 is hydrogen, C1-C4 alkyl, R4 is methyl, ethyl, R5 C1-C8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl, X is OH, NH2, C1-C8 alkyloxy and alkylamino: (linear or branched) in a separate RB in the same solvent and adding to it a dry metal hydride, agitating the contents of the flask for 30-60 min, cooling it to 4-8 °C and then adding to it the content of the first RB gradually over a period of 30-60 minutes, agitating the reaction mixture for 2-4 hrs followed by refluxing the same for 2-4 hrs cooling the reaction mixture to room temperature and agitating for 4-6 hrs followed by evaporating the organic solvent under reduced pressure, dissolving the solid mass in water and extracting the product in an organic solvent by repeated extraction and evaporating the organic solvent leads to a compound having formula (V)
(Formula Removed)

wherein:
R1 is hydrogen, halogen, C1 to C12 : alkyl, alkoxy (all linear and branched), R2 is hydrogen, C1-C8 alkyl, cyclopentyl, cyclohexyl or cumyl, R3 is hydrogen, C1-C4 alkyl R4 is methyl, ethyl R5 C1-C8alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl X is O, NH, C1-C8 alkyloxy and alkylamino: (linear or branched) and Y is tert-butyldimethylsilyl, tert-butyl-di-phenylsilyl, dimethylthexylsilyl, benzoyl, benzyl, and acetyl, and taking the compound (V) in an RB with a hydroxy deprotecting reagent and stirring the reaction mixture at room temperature for 1-3 hrs followed by addition of water and extracting the product in an organic solvent, drying the solvent with an anhydrous inorganic salt after neutralization with an inorganic base and evaporating the solvent gives the compound having formula
(I)-
3.A process as claimed in claim 2 wherein solvent used to dissolve compound (II) is
selected from dichloromethane, pyridine, dimethylformamide, tetrahydrofuran,
acetonitrile and 1-4 dioxane.
4. A process as claimed in claim 2 wherein base used to react with compound
having formula (II) is selected from imidazole, pyridine, 2,6-lutidine,
trimethylamine, mercaptobenzoxazole and alkyl substituted pyridine.
5.A process as claimed in claim 2 wherein, the hydroxy protecting group is
selected from, tert-butyl-di-methylsilylchloride, tert-butyl-di-phenylsilylchloride,
dimethylthexylsilyl chloride, acetyl chloride, benzoyl chloride, benzyl bromide,
benzoic acid, acetic anhydride and acetic acid.
6.A process as claimed in claim 2 wherein, the catalyst used is selected from imidazole, dimethyl aminopyridine, diethyl aminopyridine, dimethyl aniline, dicyclohexyl carbodimide and hydroxy benzotriazole.
7. A process as claimed in claim 2 wherein the organic solvent used for dissolving the crude mass is select from dichloromethane, chloroform, acetone, diethyl ether and benzene.
8. A process as claimed in claim 2 wherein the solvent used to dissolve the compound (III) is selected from dimethylformamide, tetrahydrofuran, acetonitrile, 1,4-dioxane and dichloromethane.
9. A process as claimed in claim 2 wherein the hindered amine having general formula (IV), added to react with compound (III) is selected from 1,2,2,6,6-pentamethyl-4-aminopiperidine, l,2,2,6,6-pentamethyl-4-piperidinol, 1,2,2,6,6-pentamethyl-4-methyl-4-aminopiperidine, l,2,2,6,6-pentamethyl-4-ethylamino piperidine

10. A process as claimed in claim 2 wherein the metal hydride is selected from sodium hydride and potassium hydride.
11. A process as claimed in claim 2 wherein the solvent used for extracting the product from the aqueous medium is selected from dichloromethane, dichloroethane, ethyl acetate, diethyl ether, benzene and n-hexane.
12. A process as claimed in claim 2, wherein the hydroxy deprotecting agent for deprotecting the compound (V) is selected from tetrabutyl ammonium fluoride, boron triflouride, boron trichloride, boron tribromide, aluminum chloride, sodium bicarbonate, aqueous ammonia, hydrochloric acid, lithium chloride and lithium aluminum hydride.
13. A process as claimed in claim 2 wherein the solvent used for extracting the product from the aqueous medium is selected from dichloromethane, dichloroethane, ethyl acetate, diethyl ether, benzene and n-hexane.
14. A process as claimed in claim 2 wherein the inert gas is selected from Nitrogen and Argon.
15. A process as claimed in claim 2 wherein the inorganic base used to neutralize the solvent fraction containing the product is selected from sodium carbonate, sodium bicarbonate, potassium bicarbonate and potassium carbonate.



Documents:

01692-delnp-2003-abstract.pdf

01692-delnp-2003-claims.pdf

01692-delnp-2003-complete specification (granted).pdf

01692-delnp-2003-correspondence-others.pdf

01692-delnp-2003-description (complete).pdf

01692-delnp-2003-form-1.pdf

01692-delnp-2003-form-18.pdf

01692-delnp-2003-form-2.pdf

01692-delnp-2003-form-3.pdf

1692-DELNP-2003-Claims-(10-10-2008).pdf

1692-DELNP-2003-Claims--(27-03-2009).pdf

1692-DELNP-2003-Correspondence-Others-(10-10-2008).pdf

1692-DELNP-2003-Description (Complete)-(10-10-2008).pdf

1692-DELNP-2003-Form-2-(10-10-2008).pdf

1692-DELNP-2003-Form-2-(27-03-2009).pdf

1692-DELNP-2003-Form-3-(10-10-2008).pdf

1692-DELNP-2003-Petition-137-(10-10-2008).pdf


Patent Number 233398
Indian Patent Application Number 01692/DELNP/2003
PG Journal Number 13/2009
Publication Date 27-Mar-2009
Grant Date 30-Mar-2009
Date of Filing 16-Oct-2003
Name of Patentee COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH
Applicant Address RAFI MARG, NEW DELHI -110 001, INDIA.
Inventors:
# Inventor's Name Inventor's Address
1 MOHITKUMAR SHROJILAL DESAI NCL, PUNE.
2 RAJ PAL SINGH NCL, PUNE.
PCT International Classification Number C07D 401/10
PCT International Application Number PCT/IN01/00190
PCT International Filing date 2001-10-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/984,624 2001-10-30 U.S.A.