FORM2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
1. Title of the invention - HYDROGENATION OF IMINES
2. Applicant(s)

(a) NAME : UNITED PHOSPHORUS LTD.
(b) NATIONALITY : An Indian Company
(c) ADDRESS : Registered office at: 3-11, GIDC, Vapi - 396195, State of Gujarat,
India and having its office at Uniphos House, 11th Road, CD. Marg, Khar (West), Mumbai - 400 052, State of Maharashtra, India
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed:

Divided out of Patent Application number 1363/MUM/2007 dated July 16.2007
FIELD OF THE INVENTION
The present invention relates to an immobilized iridium xyliphos catalyst and a process for the preparation thereof. More particularly, the present invention relates to an immobilized iridium xyliphos catalyst, a process for preparation thereof and a process for the preparation of a chloroacetamide herbicide, particularly S-Metolachlor, using said catalyst.
BACK GROUND AND PRIOR ART:
Processes for the catalytic hydrogenation of imines with homogeneous iridium catalysts have been known for a relatively long time. Catalytic processes using either homogeneous catalysts or heterogeneous catalysts have played an important role in organic synthesis. Heterogeneous catalysts are insoluble; thus they can be readily separated from the reaction mixture and generally, offer the potential for ready re-use whereas homogeneous catalysts are soluble and so difficulties can be encountered in separating the homogeneous catalyst, both the metal and the accompanying ligands, from the product. This not only presents problems with the purity of the product, but also makes the re-use of the homogeneous catalyst problematic. Over the past twenty-five years, attempts have been made to "heterogenize" the more versatile homogeneous catalysts, the primary aim being to maintain reaction activity and selectivity of the homogeneous species while at the same time significantly increasing the ease of separation from the reaction medium. Among the various homogeneous catalysts, iridium-xyliphos catalyst has been found most successful commercially in the preparation of (S)-2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1 -methylethyl) acetamide [Hans-Ulrich Blaser, Advanced Synthesis and Catalysis, 2002, 344,17-31]. The hydrogenation of imines using homogenous catalysts have been well documented under patents WO 97/05094, US 5,011,995, US 5886225 and US 6,822,118.
United States Patent No. 6 822 118 describes, in general, a process for the hydrogenation of imines with hydrogen under elevated pressure in the presence of homogeneous iridium catalysts with appropriate ligand and with or without an inert solvent, wherein the reaction mixture contains an ammonium or metal chloride, bromide or iodide and additionally an acid.

This patent also describes the use of this process in hydrogenating imine of methyl-ethyl-aniline (MEA) of the Formula (II) (R1= C2H5; R2 = CH3, R3 = H, R4 = CH3, R5 - CH2OCH3) to (S)-N-(2-ethyl-6-methyl-phenyl) -N-(l-methoxymethyI)ethylamine of the Formula (III) (R1= C2H5, R2 - CH3, R3 = H, R4 = CH3, R5 = CH2OCH3) at 50 °C under 80 bar hydrogen pressure with about 78 % enantiomeric excess (ee) using Ir(l,5-cyclooctadiene)-({(R)-l-{(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethylphenyl)phosphine)Cl] known as Ir Xyliphos catalyst, with acetic acid and toluene and conversion of the hydrogenated product of Formula (III) (R1= C2H5, R2 = CH3, R3 = H, R4 - CH3, R5 = CH2OCH3) to (S)-2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-l-methylethyl) acetamide of Formula (I) (R1= C2H5, R2 = CH3, R3 = H, R4 = CH3, R5 = CH2OCH3).
The catalysts in these homogeneous processes cannot be recovered or can be recovered only with expensive separation methods, which is always associated with undesirable losses.
PCT Publication No. WO9702232 describes a process for the hydrogenation of imines with hydrogen at increased pressure in the presence of iridium-diphosphine [XIrYZ] catalysts immobilized on a support material (organic polymers, inorganic metal oxides), a halide and an acid., wherein X is two olefin ligands or one diene ligand, Y is a ditertiary diphosphine and Z is halide.
The diphosphine Y contains at least one chiral atom, and the diphosphine is preferably an optically pure stereo-isomer (enantiomer or diastereomer), or a diastereomer pair, since optical inductions are achieved in asymmetric hydrogenations with catalysts, which contain these ligands. Ferrocenyldiphosphines are preferred ligands for fixing them to an inorganic support material like silica. The diphosphine Y is preferably bonded via silyl group to an inorganic support material which is chosen from the group consisting of silicates, semimetal or metal oxides, glasses or mixtures thereof. The polymer supports described in this patent require cumbersome synthetic processes and additionally have problems associated with polymer swelling and attendant mass transfer difficulties during their use. Also, in case of inorganic metal oxides, the ligands are not directly used for support over metal oxide but they are derivatized to silyl compounds before immobilization and due to this the process of immobilization becomes complicated and expensive.

United States Patent No. 6,005,148 describes a supported catalyst comprising a support, an anchoring agent such as a heteropoly acid or anion and a metal complex which is useful in a wide variety of organic reactions, especially hydrogenation of substituted α,β unsaturated acids and esters and α- or β- keto esters or lactones. Various methods of preparation of supported catalysts are also disclosed, for example, preparation of Rh(COD)(DIPAMP)BF4 / PTA / A1203 catalyst system where Rh(COD)(DIPAMP)BF4 is metal complex, PTA(phosphotungstic acid) as anchoring agent and Al2O3 as support material.
This patent describes the use of supported catalyst system for hydrogenation of substituted a, p-unsaturated acid or ester, hydroformylation of alkenes into their corresponding aldehydes or alcohols but not hydrogenation of imines. Also the supported Rh and Pd based catalysts described in the patent are not suitable for hydrogenation of imines to get high conversion and high enantiomeric selectivity.
Accordingly, there exists a need in the art for supported, immobilized catalyst that is capable of being recycled and reduces metal leaching into the final product so as to render the overall process environment friendly, cost effective and economical. There exists a further need in the art for supported, immobilized catalyst which enable easy separation and are capable of being recycled, which retain their activity and selectivity during the repeated usage. There exists a further need in the art for catalysts capable of being used in large scale hydrogenation processes such as processes for the preparation of amines, which are important intermediate for the preparation of chloroacetamide herbicides. One such important chloroacetamide herbicide produced on commercial scale is (S)-2-chloro-N-(2-ethyl-6-memylphenyl)-N-(2-methoxy-1-methylethyl) acetamide, S-Metolachlor (I) (R1= C2H5, R2 = CH3, R3 = H, R4 = CH3, R5 = CH2OCH3)


OBJECTS OF THE INVENTION:
An object of the present invention is to provide a catalyst system that is capable of being recycled conveniently.
Another object of the present invention is to provide a supported, immobilized catalyst system which reduces metal leaching into the final product thereby rendering the overall process environment friendly, cost effective and economical.
Yet another object of the present invention is to provide a supported, immobilized catalyst system which enables easy separation of the catalyst from a reaction mixture and which retains its activity and selectivity during the repeated, recycled usage.
Another object of the present invention is to provide a supported, immobilized catalyst system which is capable of being used in large scale hydrogenation processes such as a process for the preparation of amines.
Another object of the present invention is to provide a process for asymmetric hydrogenation of imines to amines using an immobilized catalyst system.
Yet another object of the present invention is to provide a process for the preparation of a chloroacetamide herbicide, more particularly (S)-2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-

methoxy-1-methylethyl) acetamide of Formula (I) (R1= C2H5, R2 = CH3, R3 = H, R4 = CH3, R5 = CH2OCH3).
SUMMARY OF THE INVENTION
According to an aspect of the present invention, there is provided a catalyst system comprising iridium- xyliphos ligands immobilized on alumina and a heteropolyacid.
In another aspect, the present invention provides a process for the preparation of a catalyst system comprising iridium-xyliphos ligands immobilized on alumina and a heteropolyacid, said process comprising:
(a) mixing a solution of [Ir(l,5-cyclooctadiene)Cl]2 in an organic solvent with xyliphos ligand under an inert atmosphere;
(b) stirring said mixture of step (a) at a predetermined temperature until the solution becomes clear;
(c) adding alumina and a heteropolyacid to said clear solution; and
(d) stirring said mixture of step (c) for a predetermined time under an inert atmosphere.
In yet another aspect, the present invention provides a process for hydrogenation of imines, said process comprising contacting said imine with hydrogen under elevated pressure in the presence of a provided immobilized iridium-xyliphos catalyst system.
DESCRIPTION OF INVENTION:
Therefore, in an aspect, the present invention provides a catalyst system comprising iridium-xyliphos ligands immobilized on alumina and a heteropolyacid.
Without wishing to be bound by theory, it is believed that the use of alumina and a heteropoly acid forms a covalent bond by anchoring to the catalyst thereby immobilizing the catalyst. It is further believed that such anchoring results in a high yield of the catalyst system and prevents leaching of the catalyst in the reaction solvent. This helps in the improved recovery and recycling of the catalyst on repeated usage.

In an embodiment, the preferred iridium xyliphos catalyst is [Ir(l,5-cyclooctadiene)-({(R)-l-{(S)-2-diphenylphosphino)ferroceny 1]} ethyl-di(3,5 -dimethylphenyl) phosphine) CI].
In another aspect, the present invention provides a process for the preparation of a catalyst system comprising iridium-xyliphos ligands immobilized on alumina and a heteropolyacid, said process comprising:
(a) mixing a solution of [Ir(l,5-cyclooctadiene)Cl]2 in an organic solvent with xyliphos ligand under an inert atmosphere;
(b) stirring said mixture of step (a) at a predetermined temperature until the solution becomes clear;
(c) adding alumina and a heteropolyacid to said clear solution; and
(d) stirring said mixture of step (c) for a predetermined time under an inert atmosphere.
(e) filtering the solids and drying under vacuum.
In an embodiment of the present aspect, said organic solvent is preferably selected from non-polar solvents, polar aprotic solvents and polar protic solvents. In this embodiment, said non-polar solvents are selected from the group comprising hexane, heptane, benzene, toluene, xylene; polar aprotic solvents are selected from the group comprising diethyl ether, tetrahydrofuran, 1,4- dioxane, methylene chloride, chloroform and ethyl acetate; polar protic solvents are selected from a the group comprising methanol, ethanol, isopropanol, butanol.
In another embodiment, said polar aprotic solvents are selected from 1,4-dioxane, THF, dichloromethane, acetone, acetonitrile, dimethylformamide and dimethyl sulfoxide.
In another embodiment, said polar protic solvents are selected from the group comprising acetic acid, n-butanol, isopropanol, n-propanol, ethanol, ethanol and formic acid.
In an embodiment of this aspect, said organic solvent is preferably a polar protic solvent. In a preferred embodiment, said organic solvent is methanol.
In an embodiment of this aspect, said predetermined temperature at which said mixture of step (a) is stirred varies from 20°C-50°C. In another preferred embodiment, said predetermined temperature is 30 C.

In another embodiment of this aspect, said mixture of step (d) is preferably stirred for 2-6 hours. In a preferred embodiment, said predetermined time varies from 3-4 hours.
In another embodiment of this aspect, the mixture of step (c) is stirred under an inert atmosphere. Preferably, said inert atmosphere is argon atmosphere.
Preferably, said process for the preparation of a catalyst system comprises filtering the mixture obtained at step (d) and drying the same to obtain the desired catalyst system.
In yet another aspect, the present invention provides a process for hydrogenation of imines, said process comprising contacting said imine with hydrogen under elevated pressure in the presence of a provided immobilized iridium-xyliphos catalyst system.
In an embodiment of this aspect, said immobilized iridium xyliphos catalyst system comprises iridium- xyliphos ligands immobilized on alumina and a heteropolyacid.
In an embodiment, the preferred iridium xyliphos catalyst is [Ir(l,5-cyclooctadiene)-({(R)-l-{(S)-2-diphenylphosphino)ferrocenyl] }ethyl-di(3,5-dimethylphenyl) phosphine) CI].
In yet another aspect, the present invention provides a process for asymmetric hydrogenation of an imine having formula II:

said process comprising contacting said imine having the above formula with hydrogen under elevated pressure in the presence of an immobilized iridium-xyliphos catalyst system to obtain an amine having the following formula III:


Ell
Another embodiment of the invention provides a process for the large scale production of
commercially feasible (S)-2-chloro-N-(2-ethyl-6-methylphenyI)-N-(2-methoxy-l-
methylethyl) acetamide of Formula (I) (R1= C2H51 R2 = CH3, R3 = H, R4 = CH3, R5 -CH2OCH3) known as herbicide (S)-Metolachlor and is prepared according to following scheme:

Accordingly, in yet another aspect, the present invention provides a process for the preparation of a compound having a formula I:


(1) wherein said process comprises the steps of
(a) contacting a compound having the above formula II

with hydrogen under elevated pressure in the presence of an immobilized iridium-xyliphos catalyst system to obtain an amine having the following formula III:

and
(c) reacting said compound of formula III with chloroacetylchloride in the presence of a base
a a
in a non-polar solvent at temperature 0 C - 5 C to obtain a compound of formula I.

Preferably, said non-polar solvent is toluene though other organic solvents such as polar aprotic solvents and polar protic solvents described above may also be used. The product is recovered by washing the reaction mass with water to remove the base, separating the organic layer, drying the separated organic layer free of water and distilling off the solvent under vacuum.
The imines of formula (II) are preferably ketimines and are prepared according to following scheme:

Accordingly, in yet another aspect, the present invention provides a process for the preparation of a compound of formula I:

(!)
said process comprising the steps of:
(a) reacting a compound of formula


with a ketone having the formula



To obtain a compound of formula II

and
(b) contacting said compound having the above formula II with hydrogen under elevated pressure in the presence of an immobilized iridium-xyliphos catalyst system to obtain an amine having the following formula III:


(c) reacting said compound of formula III with chloroacetylchloride in the presence of a base to obtain a compound of formula I.
Preferably, said non-polar solvent is toluene though other organic solvents such as polar aprotic solvents and polar protic solvents described above may also be used. The product is recovered by washing the reaction mass with water to remove the base, separating the organic layer, drying the separated organic layer free of water and distilling off the solvent under vacuum.
According to another preferred embodiment, the group R1 is preferably ethyl, the group R2 is preferably methyl, the group R3 is hydrogen, the group R4 is preferably methyl and the group R5 is preferably methoxymethyl.
Preferably, the heteropolyacid described in any preceding aspect or embodiment is phosphotungstic acid hydrate.
The immobilized iridium-xyliphos catalyst of the present invention is prepared as follows:
[IrCODCl]2 solution in methanol is taken in a round bottom flask and the Xyliphos ligand is added to it and the mixture is stirred at about 30 C until the solution becomes clear. Alumina and phosphotungstic acid hydrate are then added to the clear solution, and the mixture is stirred for about 3-4 hours under argon atmosphere to form the catalyst. The mass is filtered under argon and the solid is dried in vacuum.
Hydrogenation of Imines using above heterogeneous catalyst is carried out as following:
The method for hydrogenation of imines comprises adding the catalyst to the imine solution in acetic acid with tetrabutyl ammonium iodide in an autoclave and flushing it with argon; followed by flushing with hydrogen and raising the hydrogen pressure to about 80 bar,
o
temperature about 50 C and keeping the mass under stirring.
On completion of the reaction the reaction mass is filtered to get the hydrogenated product in the filtrate; and catalyst as residue on the filter.

The acetic acid is distilled off by adding toluene, under vacuum at 60 C followed by distilling the hydrogenated product remaining in the still under high vacuum to get the pure product. The catalyst from the residue on the filter is recovered by washing with methanol and drying in high vacuum.
This recovered catalyst is reusable several times and has the activity and selectivity as comparable to that of original.
Imines of the formula II used for hydrogenation are those wherein Ri is H, CM alkyl, particularly methyl or ethyl; R2 is H, CH alkyl, particularly methyl or ethyl; R3 is H, CM alkyl, particularly methyl or ethyl; R4 is methyl or ethyl; R5 is CM alkyl, more particularly methyl, ethyl, propyl, isopropyl, isobutyl or methoxymethyl.
The temperature of the reaction is 20°C to 100°C, particularly 40°C to 70°C. The pressure of the reaction is 20 to 100 bar, preferably 60 to 80 bar. Substrate to catalyst ratio is 20000 - 200000, preferably 50000 - 150000.
Following examples illustrate the process of invention but do not limit the scope of the present invention.
Raw materials used in the examples are given below:
Ir-catalyst: [IrCODCl]2: Bis(l,5-cyclooctadiene) diiridium(I)dichloride (FLUKA/ALDRICH)
Ligand: Xyliphos: (R)-l-[(S)-2(Diphenylphosphino) ferrocenyl] ethyldi (3,5-xyIyI)-phosphine (Aldrich)
Support Material: alumina: Aluminium oxide (Merck)
Anchoring Agent: HP A (heteropolyacid): phosphotungstic acid hydrate (Fluka) Tetrabutyl ammonium iodide ; Methanol; Acetic acid; Chloroacetyl chloride; 2-Methyl-6-ethyl aniline; Methoxy acetone; Substituted anilines; Toluene and Sodium hydroxide.
Example 1: Preparation of immobilized catalyst system:

In lOOmL round bottom flask, a solution of [IrCODCl]2 (10mg, 1.4 x 10"5 mole) and ligand (Xyliphos) (18mg, 2.96 x 10"5 mole) in 60ml methanol were stirred for 6hr at 30°C under argon atmosphere till it became clear with no [IrCODCl]2 in the solid form. Alumina (1.2gm) and HP A (0.24gm) were added and the mixture was stirred at 30C under argon atmosphere for 3hr.
The heterogeneous catalyst thus formed was filtered under argon atmosphere and dried in vacuum thoroughly. Catalyst Yield 1.42 g.
Example 2: General Preparation of imines:
(i) Preparation of 2-methyI-6-ethyl N-(2-methoxy-l-methylethylidene) aniline (referred
hereafter as "MEA-imine") was prepared in the following manner by using known methods
in the literature:
2-Methyl-6-ethyl aniline (540gm, 4Mole) was taken in a 2L round bottom flask. To this was
added methoxy acetone (1056gm, 12Mole). The reaction mixture was heated to 110°C and
water thus formed was continuously removed by Dean-Stark assembly.
The MEA-imine obtained was further purified by distillation to give 803.6 g (98% yield) of
the MEA-imine of Formula (II) (R1= C2H5; R2 = CH3; R3 = H; R4 = CH3; R5 = CH2OCH3)
with 99.7% purity by GLC.
(ii) Preparation of other imines:
Using the method followed in 2 (i) following imines were prepared from corresponding substituted aniline as illustrated in Table 1:
Table 1: Preparation of imines

Sr.No R1 R2 Rj R4 R5 Imine Prepared Yield
% Purity
%
1 C2H5 C2H5 H CH3 CH2OCH3 2,6-diethyI-N-[2-methoxy-1-
methylethylidine] aniline 96 99.2

2 CH3 CH3 H CH3 CH2OCH3 N-[2-methoxy-l-methylethylidene]-2,6-dimethyl aniline 94 98.9
3 H CH3 H CH3 CH2OCH3 N-[2-methoxy-l-
methylethylidene]-2-
methylaniline 92 99.15
4 C2H5 CH3 H CH3 C2H5 N- [ 1 -methy Ipropylidine]-2-ethyl-6-methyl aniline 93 98.85
5 CH3 CH3 H CH3 QH; N-[l-methylpropylidene]-2,6-dimethyl aniline 90 99.25
Example 3: Hydrogenation of imines using heterogeneous catalyst
(i) Preparation of 2-ethyl-N-(2-methoxy-l-methylethyl)-6-methylaniline
In a 100ml SS autoclave, methyl-ethyl-aniline (MEA)-imine of Formula (II) (R1= C2H5; R2 = CH3; R3 = H; R4 = CH3; R5 = CH2OCH3) (12.0g, 0.0585 mole) was diluted with acetic acid (30ml) and tetrabutyl ammonium iodide (20mg) was added to it followed by immobilized catalyst (50mg) prepared in Example 1. The autoclave containing above mixture was flushed with argon. After sealing the autoclave, it was flushed once with argon followed by twice with hydrogen. The autoclave was pressurized to 80 bar by hydrogen gas and the temperature was raised to 50 C while continuous stirring.
After 24hr when MEA-imine of Formula (II) (R1= C2H5; R2 = CH3; R3 = H; R4 = CH3; R5 = CH2OCH3) was found to be absent on checking on GLC, the autoclave was cooled to room temperature and depressurized. The reaction mass was filtered and to the filtrate was added 25 ml toluene. The mixture of toluene and acetic acid were distilled off at 60 °C and the hydrogenated product (S)-N-(2-ethyl-6-methyl-phenyl) -N-(l-methoxymethyl) ethylamine of the Formula (III) (R1=C2H5, R2=CH3, R3=H, R4=CH3, R5=CH2OCH3) was distilled under high vacuum. The quantity of distilled product obtained was 11.8 g of 99% purity (yield 98%). The amine obtained was analyzed by HPLC-UV method using chiral chromatographic "CHIRACEL ODH" column with enantiomeric excess of 80% of S configuration.
The solid catalyst was recovered from the residue on the filter after washing with methanol (10ml) and vacuum drying and reused for next 2 cycles to get amine of 99% purity and 80% enantiomeric excess of S configuration.

(ii) Hydrogenation of other imines:
Using the method followed in 3 (i), following amines were prepared by hydrogenation of corresponding imines as illustrated in Table 2.
Table 2: Hydrogenation of imines

Sr.No Ri R2 R3 R4 Rs Amine Prepared Yield % Purity
% ee
%
1 C2H5 C2Hj H CH3 CH2OCH3 2,6-diethyl-N-p-
methoxy-1-
methylethyl]aniline 97 99 76
2 CH3 CH3 H CH3 CH2OCH3 N-[2-methoxy-l-methylethyl]-2,6-dimethyl aniline 96 98.85 72
3 H CH3 H CH3 CH2OCH3 N-[2-methoxy-l-
methylethyl]-2-
methylaniline 98 99.1 24
4 C2H5 CH3 H CH3 CH2CH3 N-[ 1 -methy lpropy 1] -2-ethyI-6-methyl aniline 96.5 98.8 32
5 CH3 CH3 H CH3 CH2CH3 N-[ 1 -methylpropyl]-2,6-dimethyl aniline 95 99.1 48
Example 4: Synthesis of (S)-2-chloro-N-(2-ethyI-6-methylphenyl)-N-(2-methoxy-l-methylethyl) acetamide of Formula (I):
(S)-N-(2-ethyl-6-methyl-phenyl)-N-(l-methoxymethyl) ethylamine of Formula (III) (Ri= C2H5; R2 = CH3; R3 = H; R4 = CH3; R5 = CH2OCH3) (4g, 0.192Mole) was taken in toluene (10ml). To this was added sodium hydroxide (0.92g, 0.23Mole). The reaction was stirred for 30 mins and cooled to 0 C. Chloroacetylchloride (CAC) (2.3g, 0.2Mole) in 10ml toluene was
o
added drop wise in 30 mins, not allowing the temperature to rise above 5 C. The temperature was gradually allowed to come to room temperature and maintained for 2hr. After completion of reaction, (monitored by GLC), the reaction mixture was washed with 50ml sodium bicarbonate solution (10 %w/v), followed by washing with 50ml of hydrochloric acid solution(10 %w/v) and finally with water (50ml x 2). The organic layer was separated and dried over sodium sulphate and toluene was distilled under vacuum. The product, (S)-2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-l-methylethyl) acetamide, [Formula (I)] (Ri= C2H5; R2 = CH3; R3 = H; R4 = CH3; R5 = CH2OCH3) was obtained in 95% yield and

97% purity having 90% S-isomer (80% ee) when analyzed by HPLC method using chiral chromatographic "CHIRACEL ODH" column and UV detector at 220 nm using n-hexane and 2- propanol HPLC grade solvents mixture.

WE CLAIM
1. A process for hydrogenation of imines, said process comprising contacting said imine with hydrogen under pressure of 20-100 bar in the presence of a catalyst system comprising iridium- xyliphos ligands immobilized on alumina and a heteropolyacid.
2. A process as claimed in claims 1 wherein said iridium xyliphos catalyst is [Ir(l,5-cyclooctadiene)-({(R)-l-{(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethylphenyl) phosphine) CI].
3. A process for asymmetric hydrogenation of an imine having formula II:

said process comprising contacting said imine having the above formula with hydrogen under pressure of 20-100 bar in the presence of a catalyst system comprising iridium- xyliphos ligands immobilized on alumina and a heteropolyacid to obtain an amine having the following formula III:


4. A process for the preparation of a compound having a formula I:

(!)
wherein said process comprises the steps of
(a) contacting a compound having the formula II

with hydrogen under pressure of 20-100 bar in the presence of a catalyst system comprising iridium- xyliphos ligands immobilized on alumina and a heteropolyacid to obtain an amine having the following formula III:

and
(b) reacting said compound of formula III with chloroacetylchloride in the presence of a base in a non-polar solvent at temperature 0 C - 5 C to obtain a compound of formula I. 5. A process for the preparation of a compound of formula I:

said process comprising the steps of: (a) reacting a compound of formula

with a ketone having the formula



to obtain a compound of formula II
(b) contacting said compound having the above formula II with hydrogen under pressure of 20-100 bar in the presence of a catalyst system comprising iridium- xyliphos ligands immobilized on alumina and a heteropolyacid to obtain an amine having the following formula III:

and
( c) reacting said compound of formula III with chloroacetyl chloride in the presence of a base to obtain a compound of formula I.
6. A process as claimed in any one of claims 3-5 wherein R1 is selected from H or C1-4 alkyl, R2 is selected from H or C1-4 alkyl, R3 is selected from H or C1-4 alkyl, R4 is selected from H or C1-4 alkyl, R5 is selected from H or C1-4 alkyl.

7. A process as claimed in claim 6 wherein R1 is preferably CH3 or C2H5 R2 is preferably CH3 or C2H5; R3 is preferably CH3 or C2H5; R4 is preferably selected from CH3, C2H5, or C3H7; R5 is preferably selected from CH3, C2H5, C3H7, CH(CH3)2 or CH2 CH(CH3)2.
8. A process as claimed in any one of claims 3-7, wherein imine to catalyst ratio is 20000-200000.
9. A process as claimed in claim 8, wherein imine to catalyst ratio is 50000-150000.
10. A process as claimed in any one of claims 3-9, wherein the hydrogenation
o
temperature is 20 to 100 C.
11. A process as claimed in any one of claims 3-10, wherein the enantiomeric excess for
S-isomer of amine is 20 to 80 %.