Title of Invention

A PROCESS FOR THE PREPARATION OF THE WATER SOLUBLE PALLADIUM COMPLEX

Abstract

The invention provides a water soluble palladium complex of the general formula I wherein R1, R2, R3 are substituents on phosphine ligands selected from the group consisting of hydrogen, alkyl, arylalkyl, and cycloaliphatic at least one of which carries a sulfonic acid, and salts thereof, X is aryl or alkyl sulphonato or aryl or alkyl carboxylato or formato or halides such as Cl-, Br-, I-, N O is an anionic chelating ligand consisting of an N donor and a O" group, l<n<10 and a process for the preparation thereof.

Full Text

A water soluble palladium complex and a process for the preparation of the same Field of the invention The present invention relates to a process for the preparation of a water soluble palladium complex. More particularly, the present invention relates to a process for the preparation of a water soluble palladium complex of the general formula 1, (Formula Removed) Formula I being an anionic chelating ligand containing an N donor and a O group, wherein R1, R2 and R3 are substituents of phosphine ligand at least one of which carries a sulfonic acid or salt there of and X is a sulfonato, carboxylato or formato group, or any of the halides and supported aqueous phase catalysts thereof. The water soluble palladium complexes and supported aqueous phase catalysts prepared by the process of the present invention are useful as efficient catalysts for reactions such as carbonylation, oxidation, hydrogenation, coupling, alkylation, oligomerization, polymerization. Background of the invention Water soluble palladium complexes play an important role as catalysts for several organic transformations. One method in which such water soluble catalysts can be used is in biphasic systems; comprising the water soluble organometallic complex catalyst in aqueous phase and organic reactants and products as a water immiscible phase; thereby providing easy separation and reuse of the catalyst owing to the immiscibility of the catalyst phase with the organic substrates and products (U.S. 31812; Kuntz E.G. CHEMTECH 17, 1987, 570; EP 0107006; B. Cornils, W.A Herrmann (Eds.), Aqueous-Phase Organometallic Catalysis, Wiley-VCH, 1998, Weinheim.) Another approach is an supported aqueous hase catalysts (US 5736980, US 5935892) in which the catalytic material consists of a thin aqueous film containing the water soluble metal comlex catalyst spread over a high surface area inorganic support, such as silica (J.P. Arhancet, M.E. Davis, J.S. Merola, Be. Handon, Nature, 339, 1989, 454; K.T. Wan, M.E. Davis, Nature, 370,1994,449; K.T. Wan, M.E. Davis, J. Catal., 148,1994,1). US Patent 6069253 discloses the preparation of an anionic chelating ligand containing a N donor and O group. Objects of the invention The main object of the present invention is to provide water soluble palladium complexes and supported aqueous phase catalysts thereof that are useful catalysts for a variety or organic transformations such as carbonylation, oxidation, hydrogenation, coupling, alkylation, oligomerization, polymerization. It is another object of the invention to provide a process for the preparation of novel water soluble palladium complexes that are useful as catalysts for a variety of organic transformations. Summary of the invention Accordingly, the present invention provides a water soluble palladium complex and a process for the preparation of the same having general formula 1 (Formula Removed) Formula wherein R\, R2, RS are substituents on phosphine ligands selected from the group consisting of hydrogen, alkyl, arylalkyl, and cycloaliphatic at least one of which carries a sulfonic acid, and salts thereof, X is aryl or alkyl sulphonato or aryl or alkyl carboxylato or formato or halides such as Cl-, Br', I-, N O is an anionic chelating ligand consisting of an N donor and a O group, l Formula 11 wherein RI, R2, RS are substituents on phosphine ligands selected from the group consisting of hydrogen, alkyl, arylalkyl, and cycloaliphatic at least one of which carries a sulfonic acid, and salts thereof, X is aryl or alkyl sulphonato or aryl or alkyl carboxylato or formato or halides such as Cl,- Br-, I", N O is an anionic chelating ligand consisting of an N donor and a O group, l Formula 11 wherein R'i, R52 and R'a are substituents on the phosphine ligand selected from alkyl, aryl, arylalkyl, cycloaliphatic, X is aryl or alkyl sulfonato or aryl or alkyl carboxylate or formato or halides selected from Cl-, Br-, I-, N O is an anionic chelating ligand containing a N donor and O group, in an organic solvent with a sulfonated phosphine ligand in degassed water to form the palladium complex of formula 1 in water, separating the aqueous layer and precipitating the complex of formula 1 by adding an alcohol solvent, or if desired converting the precipitated complex of formula 1 into supported aqueous phase form by mixing the aqueous layer containing the water soluble palladium complex of formula 1 with dehydroxylated silica in a Schlenk flask, forming a wet solid, stirring the wet solid vigorously for 2h under argon, evaporating water under high vacuum at constant stirring to obtain the supported aqueous phase catalyst containing the palladium complex of the formula 1 as a dry yellow powder. In one embodiment of the invention, the precipitated complex of formula 1 is converted into the supported aqueous phase form by mixing the aqueous layer containing the water soluble palladium complex of formula 1 with dehydroxylated silica in a Schlenk flask, forming a wet solid, stirring the wet solid vigorously for 2 h under argon, evaporating water under high vacuum at constant stirring to obtain the supported aqueous phase catalyst containing the palladium complex of the formula 1 as a dry yellow powder. In another embodiment of the invention, the anionic chelating ligand in the compound of / formula I and II is an organic compound, containing a N donor and an O- group selected from the group consisting of 8-hydroxy quinoline, 2-hydroxy pyridine, 2-(2-hydroxy ethyl) pyridine, pyridyl-2-, piperidyl-2-, quinolyl-2-, isoquinolyl-1 - and isoquinolyl-3-carboxylates, particularly pyridyl-2-carboxylate, piperidyl-2 carboxylate, and 8-hydroxy quinoline. In another embodiment of the invention, the sulfonated phosphorous ligand in the compound of formula I is a sulfonated mono phosphine. In a further embodiment of the invention, the sulfonated phosphorous ligand is selected from the group consisting of tris(sodium-3-sulfonatophenyl)phosphine (TPPTS), phenyl bis(sodium-3-sulfonatophenyl)phosphine (TPPDS), diphenyl (sodium-3- sulfonatophenyl)phosphine (TPPMS), methylbis(3-sulfonatophenyl)phosphine, cyclohexylbis(sodium-3-sulfonato phenyl)phosphine, isopropylbis(sodium-3- sulfonatophenyl)phosphine, dimethyl (sodium-3-sulfonatophenyl) phosphine, dicyclohexyl-(3-sulforiatophenyl) phosphine. In another embodiment of the invention, the amount of the sulfonated phosphine ligand used per gram mole of palladium for the preparation of the palladium complex of formula I is 1-10 moles, preferably 2-3 moles. In still another embodiment the organic solvent used for the preparation of the palladium complex of formula I is selected from the group consisting of chloroform, dichloromethane and methyl ethyl ketone. In still another embodiment the alcohol solvent used for the precipitation of the palladium complex of formula I from the aqueous layer is selected from methanol and ethanol. In another embodiment the silica used for the preparation of the supported aqueous phase catalyst containing the complex of formula I is selected from porous or non-porous silica. In another embodiment the silica for the preparation of the supported aqueous phase catalyst containing the complex of formula I is preferably dehydroxylated by heating at 523 K under vacuum for 5-6 hours. Detailed description of the invention Although many water soluble palladium complexes have been reported in the literature, the water soluble complex having the formula I and the corresponding supported aqueous phase catalysts have been synthesised for the first time and there is no prior art available for synthesising these complexes and supported aqueous phase catalysts thereof. The process of the present invention described herein below with reference to examples, which are illustrative only and should not be construed to limit the scope of the present invention in any manner. EXAMPLE 1 0.0629 mmol of the palladium complex of formula II wherein R'1, R'2, R'3 = phenyl, X = p-toluenesulfonato (TsO-), N O = pyridyl-2-carboxylate (prepared as the procedure given in the patent US 6069253)} was dissolved in methyl ethyl ketone (MEK) (10 ml) and shaken vigorously with 3 equivalents of TPPTS {tris(/n-sulfophenyl)phosphine trisodium salt} in degassed water (6 ml). The yellow colour of the MEK layer disappeared and the aqueous layer became yellow in colour indicating the formation of the palladium complex of formula I in water, which was precipitated from water by adding methanol. The yellow fine suspension of the compound I was filtered under argon, washed with methanol and dried under vacuum to yield a yellow fine powder. Yield=90 % Anal. Calcd. for C31H23N Na3O,4PPdS4.6H2O: C, 34.598; H, 3.278; N, 1.301; S, 11.916; P, 2.878; Found: C, 34.05; H, 3.28; N, 1.33; S, 12.32; P, 2.50. IR (KBr) 1636 s (vc=o), 1397s (vO=c-o), 524s (vPd-N). 31P (D2O, ppm) S353Is (N trans to P), £36.13w (N cis to P). 'H (D2O, ppm) δ2.25 s (3H, tolyl CH3), S 7.2-8 m (Ph and pyridil). EXAMPLE 2 0.0629 mmol of the palladium complex of formula II wherein R'i, R*2, R(3 = phenyl, X = p-toluenesulfonato (TsO-), N O = pyridyl-2-carboxylate (prepared as the procedure given in the patent US 6069253)} was dissolved in chloroform (10 ml) and shaken vigorously with 3 equivalents of TPPTS {tris(w-sulfophenyl)phosphine trisodium salt} in degassed water (6 ml). The yellow colour of the chloroform layer disappeared and the aqueous layer became yellow in colour indicating the formation of the palladium complex of formula I, which was precipitated from water by adding methanol. The yellow fine suspension of the compound I was filtered under argon, washed with methanol and dried under vacuum to yield a yellow fine powder. Yield=92 % EXAMPLE 3 0.0629 mmol of the palladium complex of formula Ha {II in which R'1, R2, R'3 = phenyl, X = p-toluenesulfonato (TsO-), N O = pyridyl-2-carboxylate (prepared as the procedure given in the patent US 6069253)} was dissolved in methyl ethyl ketone (MEK) (10 ml) and shaken vigorously with 3 equivalents of TPPTS {tris(/w-sulfophenyl)phosphine trisodium salt} in degassed water (6 ml). The yellow colour of the MEK layer disappeared and the aqueous layer became yellow in colour indicating the formation of the palladium complex of formula I, which was precipitated from water by adding ethanol. The yellow fine suspension of the compound I was filtered under argon, washed with ethanol and dried under vacuum to yield a yellow fine powder. Yield=90 % EXAMPLE 4 0.0629 mmol of the palladium complex of formula II wherein R'i, R'2, R's = phenyl, X = p-toluenesulfonato (TsO"), NO - pyridyl-2-carboxylate (prepared as the procedure given in the patent US 6069253)} was dissolved in methyl ethyl ketone (MEK) (10 ml) and shaken vigorously with 2 equivalents of TPPTS {tris(m-sulfophenyl)phosphine trisodium salt} in degassed water (6 ml). The yellow colour of the MEK layer disappeared and the aqueous layer became yellow in colour indicating the formation of the palladium complex of formula I, which was precipitated from water by adding methanol. The yellow fine suspension of the compound I was filtered under argon, washed with methanol and dried under vacuum to yield a yellow fine powder. Yield=88 % EXAMPLE 5 0.0629 mmol of the palladium complex of formula II wherein R'1, R'2, R'3 = phenyl, X = p-toluenesulfonato (TsO-), N O = pyridyl-2-carboxylate (prepared as the procedure given in the patent US 6069253)} was dissolved in methyl ethyl ketone (MEK) (10 ml) and shaken vigorously with 1 equivalent of TPPTS {tris(/w-sulfophenyl)phosphine trisodium salt} in degassed water (6 ml). The yellow colour of the ME K layer disappeared and the aqueous layer became yellow in colour indicating the formation of the palladium complex of formula I, which was precipitated from water by adding methanol. The yellow fine suspension of the compound I was filtered under argon, washed with methanol and dried under vacuum to yield a yellow fine powder. Yield=85 % EXAMPLE 6 0.0937 mmol of the palladium complex of formula II wherein R1, R'2, R'3 = phenyl, X = p-toluenesulfonato (TsO-), N O - pyridyl-2-carboxylate (prepared as the procedure given in the patent US 6069253)} was dissolved in methyl ethyl ketone (MEK) (7 ml) and shaken vigorously with 3 equivalents of TPPTS {tris(w-sultbphenyl)phosphine trisodium salt} in degassed water (3 ml). The yellow colour of the MEK layer disappeared and the aqueous layer became yellow in colour indicating the formation of the palladium complex of formula I, in water which was added to Ig of the dehydroxylated silica in a Schlenk flask and the wet solid was stirred for 2 h under argon. Water was then evaporated under high vacuum at constant stirring. A dry yellow powder was obtained which was stored under argon. EXAMPLE 7 0. 1874 mmol of the palladium complex of formula II wherein R'1, RV R'3 = phenyl, X = p- toluenesulfonato (TsO~), N O = pyridyl-2-carboxylate (prepared as the procedure given in the patent US 6069253)} was dissolved in methyl ethyl ketone (MEK) (7 ml) and shaken vigorously with 3 equivalents of TPPTS {tris(w-sulfophenyl)phosphine trisodium salt} in degassed water (3 ml). The yellow colour of the ME;,K layer disappeared and the aqueous layer became yellow in colour indicating the formation of the palladium complex of formula 1, in water which was added to Ig of the dehydroxylated silica in a Schlenk flask and the wet solid was stirred for 2 h under argon. Water was then evaporated under high vacuum at constant stirring. A dry yellow powder was obtained which was stored under argon. EXAMPLE 8 0.04685 mmol of the palladium complex of formula 11 wherein R'1, R'2, R'3 = phenyl, X = p-toluenesulfonato (TsO-), N O = pyridyl-2-carboxylate (prepared as the procedure given in the patent US 6069253)} was dissolved in methyl ethyl ketone (MEK) (7 ml) and shaken vigorously with 3 equivalents of TPPTS (tris(/w-sulfophenyl)phosphine trisodium salt} in degassed water (3 ml). The yellow colour of the MEK layer disappeared and the aqueous layer became yellow in colour indicating the formation of the palladium complex of formula I in water which was added to1g of the dehydroxylated silica in a Schlenk flask and the wet solid was stirred for 2 h under argon. Water was then evaporated under high vacuum at constant stirring. A dry yellow powder was obtained which was stored under argon. Advantages of present invention 1. Invention of novel water-soluble palladium complexes and supported aqueous phase catalysts thereof which are stable and may be useful catalysts for a variety of organic transformations such as carbonylation, oxidation, hydrogenation, coupling, alkylation, oligomerization, polymerisation etc. 2. An easy single step process for the synthesis of novel water soluble palladium complexes with high yield. claim: 1. A water soluble palladium complex of the general formula 1 (Formula Removed) wherein RI, Ra, RS are substituents on phosphine ligands selected from the group consisting of hydrogen, alkyl, arylalkyl, and cycloaliphatic at least one of which carries a sulfonic acid, and salts thereof, X is aryl or alkyl sulphonato or aryl or alkyl carboxylato or formato or halides such as Cl-, Br-, I-, N O is an anionic chelating ligand consisting of an N donor and a O group, l Formula II 2. A process for the preparation of water soluble palladium complex having general formula 1 as described herein (Formula Removed) Formula I wherein R1, R2, R3 are substituents on phosphine ligands selected from the group consisting of hydrogen, alkyl, arylalkyl, and cycloaliphatic at least one of which carries a sulfonic acid, and salts thereof, X is aryl or alkyl sulphonato or aryl or alkyl carboxylato or formato or halides such as Cl,- Br-, I-, N O is an anionic chelating ligand consisting of an N donor and a O group, l (Formula Removed) Formula II wherein R'1, R'2 and R'3 are substituents on the phosphine ligand selected from alkyl, aryl, arylalkyl, cycloaliphatic, X is aryl or alkyl sulfonato or aryl or alkyl carboxylate or formato:or halides selected from Cl-, Br-, I-, N O is an anionic chelating ligand containing a N donor and O group, in an organic solvent with a sulfonated phosphine ligand in degassed water to form the palladium complex of formula 1 in water, separating the aqueous layer and precipitating the complex of formula 1 by adding an alcohol solvent, or if desired converting the precipitated complex of formula 1 into supported aqueous phase form by mixing the aqueous layer containing the water soluble palladium complex of formula 1 with dehydroxylated silica in a Schlenk flask, forming a wet solid, stirring the wet solid vigorously for 2h under argon, evaporating water under high vacuum at constant stirring to obtain the supported aqueous phase catalyst containing the palladium complex of the formula 1 as a dry yellow powder. 3. A process as claimed in claims 1-2 wherein the anionic chelating ligand in the compounds of formual 1 and II is an organic compound, containing a N donor and an 0 group selected from the group consisting of 8-hydroxy quinoline, 2- hydroxy pyridine, 2-(2-hydroxy ethyl)pyridine, pyridyl-2-, piperidyl-2-, quinolyl-2-, isoquinolyl-1- and isoquinolyl-3-carboxylates, particularly pyridyl- 2-carboxylate, piperidyl-2 carboxylate, and 8-hydroxyquinoline. 4. A process as claimed in claims 1-3 wherein the sulfonated phosphorous ligand in the compound of formula 1 is a sulfonated mono phosphine. 5. A process as claimed in claims 1-4 wherein the sulfonated phosphorous ligand is selected from the group consisting of tris(sodium-3-sulfonatophenyl)phosphine (TPPTS), phenyl bis(sodium-3-sulfonatophenyl)phosphine (TPPDS), diphenyl (sodium-3-sulfonatophenyl) phosphine (TPPMS), methylbis(3-sulfonatophenyl) phosphine, cyclohexylbis (sodium-3-sulfonato phenyl) phosphine, isopropylbis (sodium-3-sulfonatophenyl) phosphine, dimethyl (sodium-3-sulfonatophenyl) phosphine, and dicyclohexyl-(3-sulfonatophenyl) phosphine. 6. A process as claimed in any preceding claim wherein the amount of the sulfonated phosphine ligand used per gram mole of palladium for the preparation of the palladium complex of formula 1 is 1-10 moles. 7. A process as claimed in claims 1-6 wherein the amount of sulfonated phosphine ligand used per gram mole of palladium for the preparation of the palladium complex of formula 1 is 2-3 moles. 8. A process as claimed in any preceding claim wherein the organic solvent used for the preparation of the palladium complex of formula 1 is selected from the group consisting of chloroform, dichloromethane and methyl ethyl ketone. 9. A process as claimed in any preceding claim wherein the alcohol solvent used for the precipitation of the palladium complex of formula 1 from the aqueous layer is selected from methanol and ethanol. 10. A process as claimed in any preceding claim wherein the silica used for the preparation of the supported aqueous phase catalyst containing the complex of formula 1 is selected from porous or non-porous silica. 11. A process as claimed in claims 10 wherein the silica for the preparation of the supported aqueous phase catalyst containing the complex of formula 1 is dehydroxylated by heating at 523K under vacuum for 5-6 hours. 12. A water soluble palladium complex and a process for the preparation of the same substantially as described hereinbefore and with reference to the foregoing examples.

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