FORM 2
THE PATENTS ACT 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10; Rule 13)
1. TITLE OF THE INVENTION:
NOVEL CATALYSTS FOR PREPARATION OP AZOXYSTROBIN
2. APPLICANT(S)
(a) NAME: Excel Crop Care Limited
(b) NATIONALITY: An Indian Company
(c) ADDRESS:
184-87, Swami Vivekanand Road, Jogeshwari (West), Mumbai 400 102, Maharashtra, India.
3. PREAMBLE TO THE DESCRIPTION:
The following COMPLETE specification particularly describes the nature of this invention and the manner in which it is to be performed.

NOVEL CATALYSTS FOR PREPARATION OF AZOICYSTROBIN
FIELD OF INVENTION
Present invention relates to a method of preparation of a fungicide. More particularly, present invention relates to a method of preparation of azoxystrobin from methyl (E)-2-{2-[6-chloropyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and 2-cyanophenol using novel catalysts.
BACKGROUND AND PRIOR ART
Azoxystrobin is a broad spectrum fungicide pertaining to the p-methoxyacrylates class. Pesticidal compounds of this class are derived from naturally occurring strobilurines. Azoxystrobin is registered for use on field crops, vegetable, fruit and nut crops, ornamental plants, turfs etc. It is also registered for seed treatment of several crops and used for post-harvest treatment of banana, plantains and citrus fruits.
Process for preparation of azoxystrobin by reaction of methyl (E)-2-{2-[6-chloropyrimidin-4-yloxy]phenyl}-3-methoxyacrylate with 2-cyanophenol has been disclosed in EP0382375.
A patent application (2072/DELNP/2009) has been filed by Syngenta Ltd., wherein an improved method for preparation of Azoxystrobin using abovementioned reactants in presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a catalyst has been disclosed. However, DABCO is relatively an expensive catalyst compared to catalyst used in the process of present invention i.e., N,N,N',N'-

tetramethylethylenediamine [TMEDA]. Efficient method of
manufacturing azoxystrobin using DABCO as a catalyst is under patent protection and hence not available. This is another reason for developing alternatives to DABCO for preparation of azoxystrobin.
OBJECTS OF INVENTION
The main object of present invention is to provide novel catalysts for
preparation of Azoxystrobin by reaction of methyl (E)-2-{2-[6-
chloropyrimidin-4-yloxy]phenyl}-3-methoxyacrylate with 2-
cyanophenol.
Another object of invention is to provide a novel catalyst for preparation of Azoxystrobin which is relatively cheaper than conventionally used catalyst.
Another object of invention is to provide a method of preparation of Azoxystrobin using novel catalysts.
DETAILED DESCRIPTION OF INVENTION
Methyl (E)-2-{2-[6-chloropyrimidin-4-yloxyJphenyl}-3-methoxyacrylate reacts with 2-cyanophenol to produce azoxystrobin. The reaction is carried out in an inert solvent in presence of a base and catalyst N.N^N'-tetramethylethylenediamine [TMEDA] or 1,4-dimethyl-piperazine [DMP].
TMEDA and DMP work as effective catalysts and the reaction can be completed within comparatively shorter period of time. The method using TMEDA or DMP is suitable for large scale production of Azoxystrobin for industrial application.

EXAMPLE-1
3.04 gm 2-Cyanophenol, 10 ml DMF and 5.2 gm potassium carbonate were taken in the reactor. The mixture was heated to 60°C with stirring. 8.0 gm methyl (E)-2-{2-[6-chloropyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and 0.65 gm TMEDA (catalyst) were added. The reaction mixture was further heated to 85°C with stirring for 4.5 hrs. It was cooled to 50°C and filtered to remove salt and unreacted potassium carbonate. The salt and unreacted potassium carbonate were washed with 5 ml DMF followed by washing with 5 ml methanol. DMF along with the washings was distilled out under reduced pressure to obtain crude oily product. It was stirred with 5 ml methanol whereupon solid precipitated, which was filtered and washed with 2 ml chilled methanol. The product was dried at 85°C to obtain azoxystrobin with 72.78% yield and 93.94% purity.
EXAMPLE-2
3.04 gm 2-Cyanophenol and 10 ml DMF were taken in the reactor and the mixture was stirred. The mixture was heated to 50°C with stirring. 5.2 gm potassium carbonate was added and the temperature was increased to 60°C. 8.0 gm Methyl (E)-2-{2-[6-chloropyrimidin-4-yloxy]phenyl}-3-methoxyacrylate was added and the mixture was further heated to 80°C. 0.64 gm TMEDA (catalyst) was added and the temperature was maintained at 80°C with stirring for 3 hrs. DMF was distilled out at reduced pressure. The residue was extracted in 80 ml methylenedichloride. The organic layer was washed 3 times with 80 ml water and was dried with anhydrous sodium sulfate and was distilled out to obtain crude oily

azoxystrobin which was titurated in 15 ml heptane. Yellow solid obtained was filtered and washed with 5 ml methanol. It was dried at 85°C to obtain azoxystrobin with 85.74% yield and 93.94% purity.
EXAMPLE-3
The process as described in EXAMPLE-2 was repeated except that 3.46 gm potassium carbonate was used. The product was obtained with 87.73 % yield and 91.40% purity.
EXAMPLE-4
8.0 gm Methyl (E)-2-{2-[6-chloropyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, 3.04 gm 2-Cyanophenol, 5.2 gm potassium carbonate, 0.67 gm TMEDA (catalyst) and 10 ml DMF were taken in the reactor. The mixture was stirred and heated to 80°C and maintained at 80°C with stirring for 3 hrs. DMF was distilled out under reduced pressure. The residue was extracted in 80 ml methylenedichloride. The organic layer was washed 3 times with 80 ml water and then it was dried with anhydrous sodium sulfate. The solvent from organic layer was distilled out to obtain oily product which was titurated with 15 ml heptane. Yellow solid precipitated out which was filtered and washed with 5 ml chilled methanol and was dried at 85°C to obtain azoxystrobin with 85.74% yield and 93% purity.
EXAMPLE-5
The process as described in EXAMPLE-4 was repeated except that the catalyst used was 0.75 gm 1,1-dimethylpiperazine and reaction

temperature was maintained at 80°C for 4 hrs. The product was obtained with 87.73% yield and 91.9% purity.
EXAMPLE-6
The process as described in EZAMPLE-5 was repeated except that the reaction temperature was maintained at 90°C for 4 hrs. The product was obtained with 88.73% yield and 89.35% purity.
EXAMPLE-7
The process as described in EXAMPLE-5 was repeated except that 0.46 gm 1,1-dimethylpiperazine was used as catalyst, reaction temperature was maintained at 85°C for 5 hrs. The product was obtained with 86.73% yield and 92.73% purity.
EXAMPLE-8
The process as described in EXAMPLE-5 was repeated except that 3.45 gm potassium carbonate was added, 0.99 gm 1,1-dimethylpiperazine was used as catalyst and reaction temperature was maintained at 85°C for 5 hrs. The product was obtained with 87.73% yield and 93.06% purity.
EXAMPLE-9
8.0 gm Methyl (E)-2-{2-[6-chloropyrimidin-4-yloxy]phenyl}-3-methoxyacrylate,' 3.04 gm 2-Cyanophenol, 5.2 gm potassium carbonate, 0.70 gm 1,1-dimethylpiperazine (catalyst) and 10 ml DMF were taken in the reactor. The mixture was heated to 85°C with stirring and was maintained at 85°C for 4 hrs. It was then cooled to 50°C and filtered to remove inorganic solids. The solids were washed

with 5 ml DMF followed by washing with 5 ml methanol. DMF was distilled out under reduced pressure to obtain crude oily product which was stirred in 5 ml methanol to precipitate solid product. It was filtered and washed with 2 ml chilled methanol. The product was dried at 85°C to obtain azoxystrobin in 81.75% yield and 95.31% purity.
EXAMPLE-10
The process as described in EXAMPLE-2 was repeated except that 0.82 gm 1,1-dimethylpiperazine was used as a catalyst. The product was obtained with 87.73% yield and 92.2% purity.
EXAMPLE-11 (comparative example)
The process as described in EXAMPLE-5 was repeated except that no catalyst was used and reaction time was 6.2 hrs. The product was obtained with 66% yield and 92.7% purity.

WE CLAIM:
1. A process for preparation of azoxystrobin by reaction of methyl (E)-2-{2-[6-chloropyrimidin-4-yloxy]phenyl}-3-rnethoxyacrylate with 2-cyanophenol wherein N,N,N,N-tetramethylethylenediamine is used as a catalyst.
2. A process for preparation of azoxystrobin by reaction of methyl (E)-2-{2-[6-chloropyrimidin-4-yloxy]phenyl}-3-methoxyacrylate with 2-cyanophenol wherein 1, 4-dimethylpiperazine is used as a catalyst