Title of Invention

"A PROCESS FOR C-C COUPLING REACTION OF HELOARENES USING REUSABLE HETEROGENEOUS NANOPALLADIUM (O) CATALYST"

Abstract The present invention relates to process of forming C-C coupling reaction of haloarenes using reusable heterogeneous nanopalladium (o) catalyst, that include unreactive chloroarenes in the presence of base. The catalyst is prepared by an exchange of PdCI42-followed by reduction on the support selected from Layered double hydroxides (LDH) and S'-NR3X wherein S' is a unmodified surface support selected from resin and silica, R is an alkyl group selected from the group consisting of methyl, ethyl, propyl, butyl, X is selected from the group consisting of CI, Br, I, F, OH and OAc.
Full Text The present invention relates to a process for C-C coupling reaction of haloarenes using reusable solid support based heterogeneous nanopalladium(O) catalysts. More particularly the present invention relates to a process for C-C coupling reaction of haloarenes such as Heck, using reusable heterogeneous nanopalladium Suzuki, Sonagashira, and Stille type reactions of haloarenes by using reusable heterogeneous nanopalladium(O) catalysts on the solid support.
The reusable heterogeneous nanopalladium(O) catalysts on the solid support selected from Layered double hydroxides and Merrifield resin is prepared by a procedure as claimed and disclosed in our co-pending patent application no. NF 445-02.
This invention particularly relates to an eco-friendly process employing re-usable heterogeneous catalyst in place of soluble palladium catalysts for preparing coupling products by C-C bond formation reaction of haloarenes that include unreactive chloroarenes in the presence of base. The ligand free heterogeneous layered double hydroxides supported nanopalladium (LDH-Pd°) catalyst using the basic LDH in place of basic ligands indeed exhibits higher activity and selectivity in the C-C coupling reactions of haloarenes that include electron poor and electron rich chloroarenes in non aqueous ionic liquids (NAIL) over the homogeneous PdCh system. The coupling products find good applications as intermediates in the preparation of materials, natural products, and bioactive compounds.
There are serious disadvantages in performing the catalytic C-C bond formation reaction with iodoarenes and bromoarenes in the manufacture of olefins due to high cost of the starting materials. Despite the synthetic elegance and high turnover number, these coupling reactions suffer from serious limitations of using the expensive bromo and

iodoarenes that precluded the wide use in industry. By employing the heterogeneous catalytic system and chloroarenes as starting materials, the cost naturally comes down due to easy recovery of the catalyst and low cost of chloroarenes when compared with bromo and iodoarenes.
References may be made to the publications, Organometallics 1992, 11, 1995, Angew. Chem. Int. Ed. 1998, 37, 481, J. Organomet. Chem. 1998, 572, 93, Angew. Chem. Int. Ed Engl. 1995, 34, 2371, J. Organomet. Chem. 1999, 576, 23 wherein Heck-olefmation of chloroarenes is carried by palladium complexes under homogeneous conditions. The inherent disadvantages are difficulty in the recovery of palladium and usage of activated electron poor and nonactivated electron neutral chloroarenes.
References may be made to the publications Organometallics 1993, 12, 4734, J. Org. Chem. 1999, 64, 10, J. Am. Chem. Soc. 2001, 723,6989, Synlett, 2000, 11, 1589, J. Am. Chem. Soc. 1999,121, 2123 wherein olefins are prepared from deactivated highly electron rich chloroarenes by palladium complexes. The inherent disadvantage is the usage of expensive sterically hindered phosphine palladium complexes.
Reference may be.made to the publication Chem. Eur. J. 2000, 6, 1017 wherein Heck-olefination of deactivated highly electron rich chloroarenes is carried by palladacycle catalysts in the presence of nonaqueous liquids. The inherent disadvantages are the usage of additives and low yields.
Reference may be made to European patent DE-A 197 12 388.0,1997 wherein Heck-olefination of chloroarenes is carried by palladacycle catalyst using an additive. The inherent disadvantage is that no reaction occurs in the absence of phosphonium salt.

may be made to the publications J. Am. Chem. Soc., 1998, 120, 9722 and Angew. Chem. Int. Ed, Engl., 1998, 37, 3387 wherein biphenyls are prepared using arylchlorides with palladium catalysts. The inherent disadvantage is the usage of expensive, air-sensitive phosphine ligands.
Reference may be made to a publication J. Organometallic Chem., 1998, 557, 93 wherein biphenyls are prepared using carbene ancillary ligands with aryl bromides and activated aryl chlorides with palladium catalyst. The drawbacks are longer reaction times and yield from the aryl chloride was relatively low.
Reference may be made to a publication J. Organomet. Chem. 2001, 634, 39 wherein diarylacetylenes are prepared using heterogeneous polymer anchored bis(pyrimidine)-based palladium catalyst with chlorobenzene with impressive turnover frequency. The drawback is that it was not tried for electron rich chloroarenes.
Reference may be made to the publication Synlett, 2000, 1043 wherein arylstannanes were prepared using palladium catalyst in the presence of potassium acetate. The drawback is that the usage of aryl iodides as substrates.

Objects of the invention
The main object of the present invention is to provide a process for C-C bond coupling reactions such as Heck, Suzuki, Sonagashira, and Stille type reactions with haloarenes by using ligand free reusable heterogeneous nanopalladium (0) catalyst.

Yet another object of the present invention is to reduce the C-C coupling reaction time by employing microwave irradiation. By using microwave irradiation, the rate of C-C coupling reaction is accelerated manifold with the highest turnover frequency ever recorded both in the case of electron poor and electron rich chloroarenes.
Yet another object is to provide ligand free reusable heterogeneous nanopalladium(O) catalysts on solid support selected from LDH and S'-NR3X wherein S' is a unmodified surface support selected from resin and silica, R is an alkyl group selected from the group consisting of methyl, ethyl, propyl, butyl, X is selected from the group consisting of Cl, Br, I, F, OH and OAc.
Yet another object is to provide a process for the preparation of novel ligand free reusable heterogeneous nanopailadium (0) catalysts on solid support selected from LDH and S'-NRjX wherein S' is a unmodified surface support selected from resin and silica, R is an alkyl group selected from the group consisting of methyl, ethyl, propyl and butyl, X is selected from the group consisting of Cl, Br, I, F, OH and OAc.
Still another object of the present invention is to recover the heterogeneous palladium catalyst used inithe C-C coupling reactions such as Heck, Suzuki, Sonagashira, and Stille type reactions by simple filtration and reuse for number of cycles with consistent activity.
The novelty of the present invention lies in the C-C coupling reaction of haloarenes by using Layered double hydroxides and Merrifield resin supported nanopailadium catalysts prepared by an exchange of PdCU2" with support selected from Layered double hydroxides and Merrifield followed by reduction and its characterization.

Statement of invention
Accordingly, the present invention provides a process of forming C-C coupling reaction of haloarenes such as here in described characterized in that using ligand free reusable heterogeneous nanoplailadium (0) catalyst which comprises reacting haloarene with an organic reagent selected from the group consisting of olefin such as here in described aryl boronic acid, phenyl acetylene and tin reagent in a polar solvent in the presence of base and heterogeneous nanopalladium (0) catalyst, at a temperature ranging between 20-150°C for a period of 0.5 to 48 hrs under nitrogen atmosphere, filtering the above said reaction mixture followed by extraction and washing the resultant mass to obtain the desired C-C coupling compounds.
In an embodiment of the present invention the haloarene used is selected from the group consisting of chlorobenzene, 4-chlorobenzophenone, 4-nitrochlorobenzene, 4-acetylchlorobenzene, 4chlorobenzaldeyde, 4-chlorobenzophenone, 4-chloroanizole, 4-methylchlorobenzene and 4-chlorobenzylalcohol.
In yet another embodiment the olefin used is selected from styrene and n-butylacrylate.
In yet another embodiment the arylboronic acid used is selected from the group consisting of phynylboronic acid, 3-nitrophenylboronic acid, naphthylboronic acid, 4-fluorophynylboronic acid and 4-methyl phenylboronic acid.
In yet another embodiment the tin reagent used is selected from tributyltin hydride and allyltributyl tin.
In yet another embodiment the polar solvent used is selected from the group consisting of non aqueous ionic liquid, water, dioxance, tetraydro furon, N-methyl pyrrolidinone and any mixture thereof.


In yet another embodiment wherein the non aqueous ionic liquid used is tetra-n-butylammonium bromide.
In yet another embodiment the base used is selected from the group consisting of triethylamine, tributylamine, potassium fluoride and potassium acetate.
In still another embodiment the catalyst used is a solid support based Layered double hydroxides or Merrifield resin supported heterogeneous nanopalladium (o) catalyst.
Heterogeneous nanopalladium(O) catalysts are prepared by an exchange of PdCU2" on the support selected from LDH and S'-NR3X wherein S' is a unmodified surface support selected from resin and silica, R is an alkyl group selected from the group consisting of methyl, ethyl, propyl, butyl, X is selected from the group consisting of Cl, Br, I, F, OH and OAc in an aqueous solvent at a temperature ranging between 20 to 30 °C for a period ranging from 5 to 24 h under nitrogen atmosphere followed by filtration and reduction with hydrazine hydrate in ethanol at room temperature . Filtration gave the
desired nanopalladium(O) catalysts.
C-C bond coupling products are prepared by using the recyclable nanopalladium(0) catalysts by Heck, Suzuki, Sonagashira, and Stille type reactions of haloarenes that include unreactive chloroarenes in a under standard thermal and microwave conditions using solvents selected from nonaqueous ionic liquid , water, THF, dioxan, and NMP at a temperature ranging between 20 to 150 °C for a period 0.5 to 48 h under nitrogen atmosphere, and obtaining the pure C-C coupling products by a conventional method.

The palladium content in the catalyst ranges between 0.1 to 3 mol% with respect to the substrate. Nanopalladium (0) catalysts are recovered by simple filtration and reused for several cycles with consistent activity.
The solvents selected for the C-C bond formation reaction is selected from the group consisting of nonaqueous ionic liquid, water, 1,4-dioxane, THF, NMP or any mixture thereof. The base used is selected from the group consisting of triethylamine, tributylamine, potassium fluoride, potassium acetate.
In the present invention, we synthesized LDH, silica, resin supported nanopalladium catalysts for the first time and used in catalytic amounts for preparing coupling products by C-C bond formation reactions involving Heck-, Suzuki-, Sonogashira- and Stille type coupling of haloarenes that include chloroarenes in presence of base.
Heterogeneous nanopalladium(O) catalysts are prepared by an exchange of PdCU2" followed by reduction on silica or resin or LDH .
The nanopalladium (0) on supports is responsible for the activity of catalyst in C-C coupling reactions. "Ehb activity of heterogeneous nanopalladium catalysts is similar or higher than the homogeneous counter parts. The basic support, Mg-Al layered double hydroxides (LDH) is selected as the material of choice, which not only stabilizes the nanopalladium particles but also provides the adequate electron density to the anchored Pd° species to facilitate oxidative addition of even the deactivated electron rich chloroarenes.
Higher yields and stereoselectivities are obtained when nanopalladium catalysts are used. Incidentally this forms the first report of heterogeneous palladium catalyst
employed in the Stille type coupling. The consistent activity obtained for several cycles makes the process economical and possible for commercial realization.
The coupling products find good applications as intermediates in the preparation of materials, natural products, and bioactive compounds. Thus this invention offers the best techno-economic route for the synthesis of coupling products. Therefore, nanopalladium catalysts are better option for the C-C bond formation reaction of haloarenes that include chloroarenes.
Nanopalladium catalysts are prepared as exemplified and used in catalytic amounts for preparing coupling products by C-C bond formation reaction in presence of base in a heterogeneous way as described in the examples.
The following examples are given by way of illustration of the present invention and therefore should not be construed to limit the scope of the invention. Preparation of Nanopalladium catalysts prepared by a procedure as claimed and disclosed in our co-pending patent application no 1061DeI 2002.
Example 1 Preparation of LDH(Mg-Al-Cl) (1)
A mixture of MgCl2.6H2O ( 30.49 g, 0.15 mmol) and AlCl3.6H2O ( 12.07 g, 0.05 mmol) was dissolved in 200 ml of deionised water. To this aqueous solution, 100 ml of NaOH ( 2M) solution was slowly added at 25°C and a further amount of 2M NaOH solution was added to maintain a pH of 10 under nitrogen flow. The resulting suspension was stirred overnight at 70°C. The solid product was isolated by filtration , washed


thoroughly with deionised water and dried overnight at 80°C. All the synthetic steps were carried out using decarbonated water.
Example 2 Preparation of NajPdCU (2)
NaiPdCU was prepared by refluxing PdCh (1.77 g, 10 mmol) and sodium chloride (0.58 g, 10 mmol) in 50 mL for 4 h. The solution was filtered in hot condition to avoid NaCl contamination. Evaporation of the filtrate gave dark brown flakes (2.88 g, 98%).
Example 3
Preparation of LDH-PdCL, (3)
Mg-Al-Cl (1.5 g) was suspended in 150 mL of aqueous NaiPdCU (0.441 g, 1.5 mmol) solution and stirred at 25°C for 12 h under nitrogen atmosphere. The solid catalyst was filtered, washed thoroughly with 500 mL of water and vacuum-dried to obtain 1.752 g of LDH-PdCU (0.86 mmol of Pd per gram).
Example 4 Preparation of LDH-Pd° (4)
LDH-PdCU (1 g) was reduced with hydrazine hydrate (1 g, 20 mmol) in ethanol (10 mL) for 3 h at room temperature, filtered and washed with ethanol to give an air stable black powder (0.95 mmol of Pd per gram).
Example 5 Preparation of Resin-PdCU (5)
Resin was obtained by quaternization of triethylamine (2.1 mL, 21 mmol) with one gram of chloromethylated styrene-divinylbenzene copolymer (Merrifield resin, capacity -2.1 mequiv/g) in chloroform (20 mL) under reflux for 24 h. Quaternary

ammonium resin (1 g) was suspended in 100 mL of (0.294 g, 1 mmol) aqueous Na2PdCl4 solution and stirred at 25°C for 12 h under nitrogen atmosphere. The solid catalyst was filtered, washed thoroughly with water (300 mL) and vacuum-dried to obtain resin-PdCU (0.8 mmol of Pd per gram).
Example 6 Preparation of Resin-Pd0 (6)
Resin-PdCU (1 g) was reduced with hydrazine hydrate (1 g, 20 mmol) in ethanol (10 mL) for 3 h at room temperature, filtered and washed with ethanol to give an air stable black beads (0.87 mmol of Pd per gram).
Example 7
Preparation of Silica-PdCU (7)
Modified silica was obtained by quaternization of triethylamine (0.7 mL, 7 mmol) with bromopropylsilica (capacity 0.7 mequiv/g) in chloroform (20 mL) under reflux for 24 h. 1 g of quaternary ammonium silica was suspended in 100 mL of 0.33 mmol aqueous NajPdCU solution and stirred at 25°C for 12 h under nitrogen atmosphere. The solid catalyst was filtered, wadted thoroughly with 300 mL of water and vacuum dried to obtain SiO2- PdCU.
Example 8 Preparation of Silica-Pd0 (8)
Silica-PdCU (1 g) was reduced with hydrazine hydrate (1 g, 20 mmol) in ethanol (10 mL) for 3 h at room temperature, filtered and washed with ethanol to give an air stable black powder.

C-C Bond forming reactions
The C-C bond forming reactions were performed using LDH-Pd° catalysts to evaluate nanopalladium catalysts of the present invention. 1. Heck-Olefination.
(Figure Removed)

thermal/microwave
R = H,OCH3,N02,CH3,etc. R' = aryl, vinyl
Yield = 80 - 95% (microwave) 76-98% (thermal)
Time=0.5-lh (microwave) 10-40 h (thermal) Scheme 1
Example 9
Heck-Olefination between chlorobenzene and styrene catalysed by LDH-Pd° under thermal conditions
In a 100 mL Schlenk flask, the NAIL (3.23 g, 10 mmol) was heated to melt
(130°C) and degassed with nitrogen and vacuum prior to the addition of other reagents. After cooling the NAIL* to room temperature, LDH-Pd° (3 mol%), tri-n-butyl amine (222mg, 1.2 mmol) were added. The styrene (1.2 mmol) and chlorobenzene (1 mmol) were then added and the reaction was heated to 130°C and stirred for 10-40 h under nitrogen atmosphere. After completion of the reaction, the LDH-Pd° catalyst was filtered and washed with water and dichloromethane. After removing the solvent, the crude material was chromatographed on silica gel or recrystallized from ethanol to afford the /rans-stilbene.
Examples 10-17
The procedure was followed as in example 9 with various substrates under thermal conditions and the results are presented in Table 1.
(Table Removed)
Chloroarene (1 mmol), olefin (1.2 mmol) LDH-Pd° (3 mol%), [NBiuJBr (10 mmol), and tri-/7-butyl amine (1.2 mmol). Reactions are conducted at 130°C. b The values in parentheses refer to the homogeneous reaction conducted with PdCb under identical conditions.
Example 18
Heck-Olefination between chlorobenzene and styrene catalysed by LDH-Pd° under microwave conditions.
Styrene (1.2 mmol), chlorobenzene (1 mmol), LDH-Pd° (3 mol%), tri-n-butyl amine (222mg, 1.2 mmol) and NAIL (3.23 g, 10 mmol) were taken in a teflon vessel, closed and irradiated in a Miele Electronic M270 microwave oven at 400W and 130°C for 0.5-1 h. After completion of the reaction, the LDH-Pd° catalyst was filtered and washed with water and dichloromethane. After removing the solvent, the crude material was chromatographed on silica gel to afford the /rons-stilbene.
Examples 19-26
The procedure was followed as in example 18 with various substrates under
microwave conditions and the results are presented in Table 2.
(Table Removed)
" Chloroarene (1 mmol), olefin (1.2 mmol) LDH-Pd° (3 mol%), [NBii4]Br (10 mmol), and tri-H-butyl amine (1.2 mmol). Microwave power 400W and temperature 130°C.
Examples 27-32
In an effort to compare the reactivity of LDH-Pd° with other heterogeneous catalysts namely Pd/C, Pd/SiOj, resin-Pd0 and Pd/A^Os in the Heck-olefination, separate experiments were conducted under identical conditions with the same ingredients and the results are summarized in Table 3. The activity of various catalysts in the Heck-olefination of 4-chloroanisole is found to be in the order: LDH-Pd°>resin-Pdft>Pd/OPd/Al2O3>Pd/SiO2. These results indicate that the basic support, LDH facilitates the oxidative addition of Pd° with 4-chloroanisole and eventually the Heck-olefination reaction. »
The procedure was followed as in example 9 with various catalysts between 4-chloroanisole and styrene under thermal conditions and the results are presented in
(Table Removed)
" 4-chloroanisole (1 mmol), olefin (1.2 mmol), Palladium catalyst (3 mol%), [NBu«]Br 3.23 g (10 mmol), and tributylamine (1.2 mmol) were stirred at 130°C for 40 h.
2. Suzuki cowplng
B(OH)2
Scheme! A LDH-PdO
O
base, 100°C R
Example 33
Suzuki coupling between chlorobenzene and phenylboronic acid catalysed by LDH-
Pd°
Chlorobenzene (lmmol), phenylboronic acid (1.5 mmol), potassium fluoride (3 mmol), LDH-Pd°(l mol%) and 1,4-dioxane-water (5:1, 5 mL) were charged in a round-bottomed flask. Reactions were carried out at 100°C for 10 h. After completion of the reaction (monitored by TLC), the catalyst was filtered and the reaction mixture was poured into water and the aqueous phase was extracted with ether. After drying, the corresponding product was purified by crystallization from diethyl ether-pentane.
Examples 34-40 The procedure was followed as in example 33 and the results are given in Table 4.
(Table Removed)
Chloroarene (1 mmol), arylboronic acid (1.5 mmol), LDH-Pd° (1 mol%) and KF (3 mmol), 100°C, 10 h. All the reactions were carried out with 1,4-dioxane-water (5:1,5 mL ) as solvent. * Under NAIL conditions, 8 h.
3. Sonogashira Coupling
Scheme 3.
Example 41
Sonogashira coupling between chlorobenzene and phenylacetylene catalysed by L0H-Pd°
To a stirred slurry of chlorobenzene (1 mmol), cuprous iodide (7.6mg, 0.04 mmol), and LDH-Pd° (1 mol%), in THF (2 mL) and water (4 mL) was added
triethylamine (152 mg, 1.5 mmol). A solution of 1.25 mmol of phenylacetylene in THF (2 mL) was then added over 2 h. After completion of the reaction, the solvent was evaporated, and the residue was treated with pentane. The solution was filtered to obtain the catalyst and evaporation of the solvent gives the coupling product.
Examples 42-43
The procedure was followed as in example 41 and the results are given in Table 5.
(Table Removed)
a Chloroarene (1 mmol), phenylacetylene (1.1 mmol), LDH-Pd° (1 mol%), Et3N (1.5 mol), 80°C. All reactions were carried out with THF-water (1:1,8 mL) as solvent system. * Under NAIL conditions.
4. Stille type coupling
Cl
LDH-Pd°(1 mol%) _ _
Bu3Sn—R1— »~ R—(O>—SnBu3
° , 5o°c
Scheme 4

Example 44
Stiile type couping between chlorobenzene and tributyltin reagent catalysed by LDH-Pd°
A round-bottomed flask was charged with LDH-Pd° (1 mol%), potassium acetate (294mg, 3 mmol), and NMP (4 ml). To this 4-chloroanisole (1 mmol) and tributyltin hydride (2 mmol) were added successively, and the mixture was stirred at 50° C for 16 h. The reaction mixture was diluted with benzene, washed with water and catalyst was collected for next cycle.
Examples 45-49 The procedure was followed as in example 44 and the results are given in Table 6.
(Table Removed)
" Chloroarene (1 mmol), trialkyltin reagent (2 mmol), potassium acetate (3mmol), LDH-Pd° (2 mol%). All the reactions were carried out with NMP as solvent, 50°C, 16 h. * Under NAIL conditions, 12 h.
The main advantages of the present invention are:
1. A novel wA ecofnendly process for the synthesis of coupling products from
haloarenes that include highly unreactive chloroarenes by C-C bond formation is
presented.
2. The present process dispenses the use of soluble palladium catalysts instead a
heterogeneous reusable LDH-Pd(O) is used.
3. Nanopailadium catalyst, LDH-Pd(O) is prepared and used as heterogeneous catalyst for
the synthesis of coupling products by C-C bond formation reactions. The use of
heterogeneous nanopalladium catalyst precludes the presence of palladium in traces
with the product
4. The stereoselectivity and the yields are good.
5. The work-up procedure is simple.
6. The catalyst is subjected to many recycles, which displayed consistent activity.
7. The present process is environmentally safe since there is no disposal problem.
8. The process is economical.

We claim
1. A process of forming C-C coupling reaction of haloarenes such as herein described characterized in that using ligand free reusable nanopalladium (o) catalyst which comprises reacting haloarene with an organic reagent selected from the group consisting of olefin such as herein described, aryl boronic acid, phenyl acetylene and tin reagent in a polar solvent selected from non aqueous ionic liquid, THF, dioxane, water, NMP in the presence of base and heterogeneous nanopalladium (0) catalyst at a temperature ranging between 20 to 150°C for a period ranging from 0.5 to 48 h under nitrogen atmosphere, filtering the above said reaction mixture followed by extraction and washing the resultant mass to obtain the desired C-C coupling compounds.
2. A process as claimed in claim 1, wherein the haloarene used is selected from the group consisting of chlorobenzene, 4-nitrochlorobenzene, 4-acetylchlorobenzene, 4-chlorobenzaldehyde, 4-chlorobenzophenone, 4-chloroanisole, 4-methylchlorobenzene and 4-chlorobenzylalcohol.
3. A process as claimed in claims 1 or 2, wherein the olefin used is selected from styrene and n-butylacrylate.
4. A process as claimed in any one of claims 1 to 3, wherein the aryl boronic acid used is selected from the group consisting of phenylboronic acid, 3-nitrophynylboronic acid, napthylboronic acid, 4-fluorophynylboronic acid and 4-methyl phynylboronic acid.
5. A process as claimed in any one of claims 1 to 4, wherein the tin reagent used is selected from tributyltin hydride and allyltributyl tin.
6. A process as claimed in claim 1, wherein the polar solvent used is selected from the group consisting of nonaqueous ionic liquid, water, dioxane, tetrahydrofuran, N-methyl pyrrolidinone or any mixture thereof.
7. A process as claimed in claims 1-6, wherein the non-aqueous ionic liquid used is tetra-n-butlylammonioum bromide.
8. A process as claimed in claims 1-7, wherein the base used is selected from the group consisting of triethylamine, tributylamine, potassium fluoride, potassium acetate.
9. A process as claimed in claims 1-8, wherein the catalyst used is a solid support based Layered double hydroxides or Merrifield resin supported heterogeneous nanopalladium (o) catalyst.
10. A process for C-C coupling reaction of haloarenes using ligand free reusable nanopalladium (o) catalyst substantially as herein described with reference to the exaples and drawing accompanying this specification.

Documents:

1060-DEL-2002-Abstract-(16-03-2009).pdf

1060-DEL-2002-Abstract-(23-10-2008).pdf

1060-del-2002-abstract.pdf

1060-DEL-2002-Claims-(16-03-2009).pdf

1060-DEL-2002-Claims-(23-10-2008).pdf

1060-del-2002-claims.pdf

1060-DEL-2002-Correspondence-Others-(16-03-2009).pdf

1060-DEL-2002-Correspondence-Others-(23-10-2008).pdf

1060-del-2002-correspondence-others.pdf

1060-del-2002-correspondence-po.pdf

1060-DEL-2002-Description (Complete)-(16-03-2009).pdf

1060-DEL-2002-Description (Complete)-(23-10-2008).pdf

1060-del-2002-description (complete).pdf

1060-DEL-2002-Form-1-(16-03-2009).pdf

1060-del-2002-form-1.pdf

1060-del-2002-form-18.pdf

1060-DEL-2002-Form-2-(16-03-2009).pdf

1060-DEL-2002-Form-2-(23-10-2008).pdf

1060-del-2002-form-2.pdf

1060-del-2002-form-3.pdf


Patent Number 233696
Indian Patent Application Number 1060/DEL/2002
PG Journal Number 17/2009
Publication Date 24-Apr-2009
Grant Date 01-Apr-2009
Date of Filing 22-Oct-2002
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 MADHI SATEESH INSTITUTE OF CHEMICAL TECHNOLOGY, HYDERABAD-5,INDIA
2 BOYAPATI MANORANJAN CHOUDARY INSTITUTE OF CHEMICAL TECHNOLOGY, HYDERABAD-5,INDIA
3 NAIDU SREENIVASA CHOWDARI INSTITUTE OF CHEMICAL TECHNOLOGY, HYDERABAD-5,INDIA
4 MANNEPALLI LAKSHMI KANTAM INSTITUTE OF CHEMICAL TECHNOLOGY, HYDERABAD-5,INDIA
5 BOJJA SREEDHAR INSTITUTE OF CHEMICAL TECHNOLOGY, HYDERABAD-5,INDIA
PCT International Classification Number C07C 17/18
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA