A FUNGICIDAL COMPOUND AND PROCESS OF PREPARATION THEREOF

Abstract

The present invention relates to a fungicidal sulfenyl phthalimide compound of formula (I) and a compound of formula (II) wherein said compound of formula (I) and formula (II) are substantially free from unwanted impurity. Particularly the present invention relates to a process of preparation of compounds of formula (I) and (II) substantially free from unwanted impurity.

Claims

1. A process for preparation of a fungicidal sulfenyl phthalimide compound of formula (I) ##STR00010## wherein K together with the two contiguous linking carbon atoms, forms a 6-membered fused aromatic ring or a fused cyclohexene ring; said process comprising: (a) reacting an organosulphur compound with chlorine to form a sulfenyl compound of formula (II); and ##STR00011## (b) converting said sulfenyl compound of formula (II) to the fungicidal sulfenyl phthalimide compound of formula (I) which is substantially free from haloalkane impurities.

2. The process as claimed in claim 1, wherein said step (a) is carried out in the presence of an aqueous acidic medium and the sulfenyl compound of formula (II) is further treated with an aromatic hydrocarbon to obtain a pure sulfenyl compound of formula (II) substantially free from haloalkane impurities.

3. The process as claimed in claim 1, wherein said step b) comprises reacting the sulfenyl compound of formula (II) with a phthalimide or phthalimide derivative compound to obtain the sulfenyl phthalimide compound of formula (I) substantially free from haloalkane impurities ##STR00012## .

4. The process as claimed in claim 3, wherein said process is carried out in the presence of in an aqueous alkaline medium and an aromatic hydrocarbon to obtain the sulfenyl phthalimide compound substantially free from haloalkane impurities.

5. The process as claimed in claim 1, wherein said haloalkene impurities are selected from carbon tetrachloride, dichloro(chlorosulfanyl)methanesulfonyl chloride, and mixtures thereof.

6. The process as claimed in claim 1, wherein said organosulphur compound is selected from carbon disulfide, carbonyl sulphide, and thiophosgene.

7. The process as claimed in claim 2, wherein the acid used for acidic solution is selected from hydrochloric acid, phosphoric acid, and sulfuric acid.

8. The process as claimed in claim 4, wherein the alkali used for the aqueous alkaline medium is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, and potassium carbonate.

9. The process as claimed in claim 2, wherein said aromatic hydrocarbon is selected from toluene, chlorobenzene, ethyl benzene, propyl benzene, and xylene.

10. The process as claimed in claim 1, wherein said step a) is carried out at a temperature in the range from 5 to 20° C.

11. The process as claimed in claim 1, wherein said step b) is carried out at a temperature in the range from 0 to 10° C.

12. The process as claimed in claim 1, comprising preparing the fungicidal sulfenyl phthalimide compound of formula (I) by a) reacting carbon disulphide with chlorine in an aqueous acidic solution to obtain perchloromethyl mercaptan and treating the perchloromethyl mercaptan with an aromatic hydrocarbon to obtain perchloromethyl mercaptan which is substantially free from haloalkane impurities; and ##STR00013## b) reacting pure compound of formula (II) in an aromatic hydrocarbon solvent with phthalimide or a phthalimide derivative compound in an aqueous alkaline medium to obtain the sulfenyl phthalimide compound of formula (I) substantially free from haloalkane impurities. ##STR00014##

13. The process as claimed in claim 1, wherein said compound of formula (II) and said compound of formula of (I) are substantially free from carbon tetrachloride impurity.

14. The process as claimed in claim 13, wherein said carbon tetrachloride impurity is less than 0.05% in the process.

15. The process as claimed in claim 1, wherein said compound of formula (II) and said compound of formula of (I) obtained are about 98% pure.

16. The process as claimed in claim 1, wherein said sulfenyl phthalimide compound of formula (I) is selected from 3a,4,7,7a-tTetrahydro-N-(trichloromethanesulphenyl)phthalimide and N- (T-trichloromethanesulpheny l)phthalimide .

17. The process as claimed in claim 16, wherein said 3a,4,7,7a-tetrahydro-N- (trichloromethanesulphenyl)phthalimide compound is prepared by (a) reacting an organosulphur compound with chlorine in the presence an aqueous acidic solution to obtain crude perchloromethyl mercaptan; (b) isolating pure perchloromethyl mercaptan by treating crude perchloromethyl mercaptan of step (a) with an aromatic hydrocarbon solvent; and (c) reacting the pure perchloromethyl mercaptan with tetrahydropthalimide in the presence of an aqueous alkaline medium to obtain 3a, 4, 7, 7a- tetrahy-dro -N-(trichloromethanesulpheny l)phthalimide compound substantially free from haloalkene impurities.

18. The process as claimed in claim 16, wherein said N-(trichloromethanesulphenyl)phthalimide compound is prepared by (a) reacting carbon disulfide with chlorine in an aqueous acidic solution to obtain crude perchloromethyl mercaptan; (b) isolating pure perchloromethyl mercaptan by treating the crude perchloromethyl mercaptan obtained in step (a) with an aromatic hydrocarbon solvent and (c) reacting pure sulfenyl compound in aromatic hydrocarbon with a phthalimide compound in an aqueous alkaline medium to obtain the N-(trichloromethanesulphenyl)phthalimide compound substantially free from haloalkene impurities.

19. The process as claimed in claim 1, wherein the haloalkene impurity is carbon tetrachloride.

20. A process for preparation of a sulfenyl compound of formula (II) comprising (a) reacting an organosulphur compound with chlorine in an aqueous acidic solution to obtain a crude sulfenyl compound; and (b) treating the crude sulfenyl compound of step (a) with an aromatic hydrocarbon solvent and isolating the pure sulfenyl compound of formula (II) substantially free from haloalkane impurities.

21. The process as claimed in claim 20, comprising reacting carbon disulfide with chlorine to obtain perchloromethyl mercaptan and treating the perchloromethyl mercaptan with toluene to obtain pure perchloromethyl mercaptan substantially free from haloalkane impurities.

22. A fungicidal sulfenyl phthalimide compound of formula (I) substantially free from haloalkane impurities, ##STR00015## wherein K together with the two contiguous linking carbon atoms forms a fused aromatic ring or a fused cyclohexene ring.

23. The compound as claimed in claim 22, wherein said compound of formula (I) is substantially free from haloalkane impurities is obtained by treating crude compound of formula (I) with an aromatic hydrocarbon. .

24. The compound as claimed in claim 23, having a particle size distribution D50 of less than about 80 microns and carbon tetrachloride impurity less than 0.05%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0048] While several embodiments of the present invention have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the functions and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the present invention.

[0049] Surprisingly, inventor of the present invention found that a fungicidal sulfenyl phthalimide compounds for formula (I), can be obtained in the substantially pure form with negligible haloalkane impurities, if sulfenyl compound is made by means of chlorination of carbon disulfide, followed by treatment of the obtained crude sulfenyl compound with aromatic hydrocarbons; and reacting sulfenyl compound with phthalimide or phthalimide derivative and further treating with aromatic hydrocarbons to obtain substantially pure sulfenyl phthalimide compound.

[0050] Aromatic hydrocarbon treatment used during synthesis of both, sulfenyl compound and sulfenyl phthalimide compounds helps in reducing haloalkane impurities which ultimately leads to substantially pure sulfenyl phthalimide compounds.

[0051] Advantageously the present invention has achieved improvements in the production of sulfenyl phthalimide compounds and derivative compounds, for example captan, and folpet via the use of aromatic hydrocarbons which are believed to minimize the formation of the undesirable haloalkane impurities.

[0052] Broadly, present invention contemplates a fungicidal sulfenyl phthalimide compound substantially pure from haloalkane impurities and process of preparing fungicidal sulfenyl phthalimide compound substantially pure from haloalkane impurities using aromatic hydrocarbons. The process contemplated by this invention is further explained by the following reaction scheme.

[0053] Step I:

##STR00004##

[0054] Step II:

##STR00005##

[0055] In accordance with the present invention, fungicidal sulfenyl phthalimide compound of formula (I) describe some of the preferred compounds wherein said compound of formula (I) represented as the structure given below is substantially free from haloalkane impurities is,

##STR00006##

wherein K together with the two contiguous linking carbon atoms, forms a fused 6-membered aromatic ring a or a fused cyclohexene ring.

[0056] In an embodiment the present invention provides a compound of formula I wherein K together with the two contiguous linking carbon atoms, forms a fused cyclohexene ring (that is substantially free from haloalkane impurity and process for preparation thereof wherein said compound of formula (I) 3a,4,7,7a-Tetrahydro-N-(trichloromethanesulphenyl)phthalimide and is represented as below:

##STR00007##

[0057] In an embodiment the present invention provides a compound of formula I wherein K together with the two contiguous linking carbon atoms, forms a fused aromatic ring that is substantially free from haloalkane impurities and process for preparation thereof wherein said compound of formula (I) is N-(Trichloromethanesulphenyl)phthalimide represented as below:

##STR00008##

[0058] According to an embodiment of the present invention, there is provided a compound of formula (II) substantially free from haloalkane impurity and process for preparation thereof.

##STR00009##

[0059] In accordance with the present invention, the compound of formula (II) is also known as Trichloromethane sulfenyl chloride or Perchloronemethylmercaptan (PCMM).

[0060] In accordance with the present invention, a fungicidal sulfenyl phthalimide compound of formula (I) is substantially free from haloalkane impurities.

[0061] In accordance with the present invention, a fungicidal sulfenyl phthalimide compound of formula (I) substantially free from haloalkane impurities refers to a compound of formula (I) with less than 0.05%, preferably less than 0.01% of haloalkane impurity (by Gas Chromatography).

[0062] In accordance with the present invention, a sulfenyl compound of formula (II) is substantially free from haloalkane impurities.

[0063] In accordance with the present invention, a sulfenyl compound of formula (II) substantially free from haloalkane impurities refers to compound of formula (II) with less than 0.10, preferably less than 0.08% of haloalkane impurities ( by Gas Chromatography).

[0064] According to an embodiment of the present invention, the haloalkane impurities refers to unwanted impurities belong to the group comprising of carbon tetrachloride and dichloro(chlorosulfanyl)methanesulfonyl chloride or mixture thereof that are generated during the process of synthesis of sulfenyl compound or sulfenyl phthalimide compounds.

[0065] Typically, according to a preferred embodiment of the present invention, the haloalkane impurity is carbon tetrachloride.

[0066] According to an embodiment of the present invention, the haloalkane impurity present in sulfenyl phthalimide may be any impurities including reaction byproducts, intermediates, starting materials, and solvents.

[0067] According to an embodiment of the present invention, haloalkane impurities are capable of being removed azeotropically, such as by vacuum distillation, heat, or low-pressure evaporation.

[0068] According to an embodiment of the present invention, haloalkane impurity is preferably removed by distillation.

[0069] According to an embodiment of the present invention, a process for the synthesis of fungicidal sulfenyl phthalimide compound of formula (I) which is substantially free from haloalkane impurities wherein, said process comprises steps of: [0070] (a) reacting an organosulphur compound with chlorine to form sulfenyl compound and treating sulfenyl compound with aromatic hydrocarbon to remove haloalkane impurities to obtain pure sulfenyl compound of formula (II) and [0071] (b) reacting sulfenyl compound of formula (II) in an aromatic hydrocarbon with phthalimide or pthalimide derivatives to obtain pure sulfenyl phthalimide compound of formula (I).

[0072] In an embodiment, step (a) is carried out in presence of aqueous acidic medium and sulfenyl compound is further treated with aromatic hydrocarbon solvent to obtain pure sulfenyl compound of formula (II) substantially free from haloalkane impurities.

[0073] In an embodiment, step b) is carried out in presence of in an aqueous alkaline medium and sulfenyl phthalimide compound is further treated with aromatic hydrocarbon to obtain pure sulfenyl phthalimide compound (I) substantially free from haloalkane impurities.

[0074] According to an embodiment of the present invention, a process for the synthesis of fungicidal sulfenyl phthalimide compound of formula (I) which is substantially free from haloalkane impurity wherein, said process comprises steps of: [0075] (a) reacting organosulphur compound with chlorine to obtain crude sulfenyl compound; [0076] (b) treating crude sulfenyl compound of step (a) with aromatic hydrocarbon to remove haloalkane impurity and obtaining sulfenyl compound of formula (II); [0077] (c) reacting sulfenyl compound of formula (II) with phthalimide or pthalimide derivatives to obtain sulfenyl phthalimide compound of formula (I);

[0078] According to an embodiment of the present invention, a process for the synthesis of 3a,4,7,7a-Tetrahydro-N-(trichloromethanesulphenyl)phthalimide compound of formula (I) which is substantially free from haloalkane impurities wherein, said process comprises steps of: [0079] (a) reacting organosulphur compound with chlorine to obtain crude sulfenyl compound; [0080] (b) treating crude sulfenyl compound of step (a) with aromatic hydrocarbon to remove haloalkane impurities and obtaining sulfenyl compound of formula (II); [0081] (c) reacting sulfenyl compound of formula (II) in an aromatic hydrocarbon with tetrahydropthalimide to obtain 3a,4,7,7a-Tetrahydro-N-(trichloromethanesulphenyl)phthalimide compound of formula (I).

[0082] In step a) the organosulphur compound is carbon disulfide and sulfenyl compound is perchloromethyl mercaptan. Typically, the step a) is carried out at 5 to 10° C. After completion of the reaction of step a) the reaction mass is treated aromatic hydrocarbon solvent. The aromatic hydrocarbon solvent used is selected from the group comprising toluene, chlorobenzene, ethyl benzene, propyl benzene, xylene and the like. The solution thus obtained is then subjected to distillation to remove the unwanted impurities and isolating pure sulfenyl compound which can be directly used for preparation of sulfenyl phthalimide compound of formula (I) without further purification.

[0083] In step c) pure sulfenyl compound as obtained in step b) is reacted with tetrahydropthalimide in aqueous basic medium. Typically, the reaction is performed at low temperature preferably at 0 to 10° C., more preferably at 0 to 5° C. for 1 to 5 hours preferably for about 1 to 2 hours. The reaction mass is then charged with aromatic hydrocarbon solvent and the mixture is heated to temperature in the range from 50 to 100° C., preferably at 70-80° C. and pure sulfenyl phthalimide compound is isolated from the mixture having high purity and high yield as well as reduced unwanted haloalkene impurities preferably to below 0.01%.

[0084] According to an embodiment of the present invention, a process for the synthesis of N-(Trichloromethanesulphenyl)phthalimide compound of formula (I) which is substantially free from haloalkane impurities wherein, said process comprises steps of: [0085] (a) reacting organosulphur compound with chlorine to form sulfenyl compound; [0086] (b) treating sulfenyl compound of step (a) with aromatic hydrocarbon to remove haloalkane impurities and obtaining sulfenyl compound of formula (II); [0087] (c) reacting sulfenyl compound of formula (II) with phthalimide to obtain N-(Trichloromethanesulphenyl)phthalimide compound of formula (I).

[0088] According to an embodiment of the present invention, a process for the synthesis of sulfenyl compound of formula (II) which is substantially free from haloalkane impurities wherein, said process comprises steps of: [0089] (a) reacting organosulphur compound with chlorine to obtain crude sulfenyl compound; [0090] (b) treating crude sulfenyl compound of step (a) with aromatic hydrocarbon to remove haloalkane impurities and obtaining sulfenyl compound of formula (II) which is substantially free from haloalkane impurities.

[0091] In another aspect of the present invention, a process for the synthesis of fungicidal sulfenyl phthalimide compound of formula (I) which is substantially free from haloalkane impurities wherein, said process comprises:

[0092] reacting sulfenyl compound of formula (II) with pthalimide or phthalimide derivative and obtaining fungicidal sulfenyl phthalimide compound of formula (I);

[0093] According to an embodiment of the present invention, a process for the synthesis of 3a,4,7,7a-Tetrahydro-N-(trichloromethanesulphenyl)phthalimide compound of formula (I) which is substantially free from haloalkane impurities wherein, said process comprises:

[0094] reacting sulfenyl compound of formula (II) obtained according to the present process with tetrahydropthalimide and obtaining pure 3a,4,7,7a-Tetrahydro-N-(trichloromethanesulphenyl)phthalimide compound of formula (II) substantially free from haloalkane impurities.

[0095] According to an embodiment of the present invention, organosulphur compound is selected from the group comprising of carbon disulfide, carbonyl sulphide, thiophosgene and the like.

[0096] According to preferred embodiment of the present invention, organosulphur compound carbon disulfide.

[0097] According to an embodiment of the present invention, acid medium utilized in step (a) to form sulfenyl compound of formula (II) is selected from the group comprising of hydrochloric acid (HCl), phosphoric acid, sulfuric acid.

[0098] According to preferred embodiment of the present invention, acid medium utilized in step (a) to form sulfenyl compound of formula (II) is hydrochloric acid (HCl).

[0099] According to an embodiment of the present invention, alkaline medium utilized in step (b) to form sulfenyl phthalimide compound of formula (I) is selected from the group comprising of sodium hydroxide (NaOH), potassium hydroxide (KOH), Lithium hydroxide (LiOH), potassium carbonate (K.sub.2CO.sub.3) and the like.

[0100] According to preferred embodiment of the present invention, alkaline medium utilized in step (b) to form sulfenyl phthalimide compound of formula (I) is sodium hydroxide (NaOH).

[0101] According to an embodiment of the present invention, aromatic hydrocarbon used for synthesis of sulfenyl phthalimide compound of formula (I) and sulfenyl compound of formula (II) are selected from the group comprising of toluene, chlorobenzene, ethyl benzene, propyl benzene, xylene and the like.

[0102] According to preferred embodiment of the present invention, aromatic hydrocarbon used for synthesis of sulfenyl phthalimide compound of formula (I) and sulfenyl compound of formula (II) is toluene.

[0103] Accordingly, a fungicidal sulfenyl phthalimide compound of formula (I), obtained by the present process as described above is substantially free from haloalkane impurities.

[0104] Preferably, 3a,4,7,7a-Tetrahydro-N- (trichloromethanesulphenyl)phthalimide obtained by the present process is substantially free from haloalkane impurities.

[0105] Preferably, N-(Trichloromethanesulphenyl) phthalimide obtained by the present process is substantially free from haloalkane impurities.

[0106] In an embodiment, the process according to the present invention provides fungicidal sulfenyl phthalimide having particle size distribution D.sub.10 of less than about 23.101 microns.

[0107] In an embodiment, the process according to the present invention provides fungicidal sulfenyl phthalimide having particle size distribution D.sub.50 of less than about 72.223 microns.

[0108] In an embodiment, the process according to the present invention provides fungicidal sulfenyl phthalimide having particle size distribution D.sub.90 of less than about 172.728 microns.

[0109] According to the invention the compound of formula (1) is obtained in high yield and has high purity of more than 98.5%. The present process is simple, easy and convenient to carry out, efficient, economical and also industrially and commercially viable.

[0110] According to an embodiment of the present invention, fungicidal sulfenyl phthalimide compound may be used in any kind of solid or liquid formulation meant for agrochemical application along with other optional components including but not limited to surfactants, dispersing agents; wetting agents; antifoaming agents; antimicrobial agents; antioxidants; buffers; dyes; perfumes; stabilizing agents; and water-soluble salts.

[0111] According to an embodiment of the present invention, fungicidal sulfenyl phthalimide compound may also be mixed with other agrochemically acceptable ingredients, for example fertilizers such as ammonium nitrate, urea, potash, and superphosphate; phytotoxicants and plant growth regulators; safeners; and pesticides.

[0112] According to an embodiment present invention provides a fungicide composition comprising a fungicidal sulfenyl phthalimide compound of formula (I) substantially free from haloalkane impurities prepared according to present process. In another embodiment the present invention provides a method of treating fungal infection by applying to the locus a fungicidal sulfenyl phthalimide compound of formula (I) substantially free from haloalkane impurities prepared according to present process.

[0113] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope. The process of preparing sulfenyl phthalimide compound is illustrated in the following examples:

EXAMPLES

Example 1 Synthesis of 3a,4,7,7a-Tetrahydro-N-(Trichloromethanesulphenyl) Phthalimide

[0114] Step 1: In 1664 g water, 974 g (30%) aqueous HCl solution and 380 g carbon disulfide was charged at 5-10° C. and chlorine gas was purged for 22-24 hrs at same temperature. After completion of reaction, layers were separated, organic mass was collected and toluene (210 gm) was added and further organic layer was washed two times with 250 gm water. 905 g crude Perchloromethyl Mercaptan (PCMM) toluene solution was obtained. Distillation was performed of crude PCMM toluene solution on 3 feet packed column to remove low boiler and haloalkane impurity, carbon tetrachloride (CTC) along with toluene under vacuum. The PCMM toluene solution thus obtained was further taken for step 2. Final sulfenyl compound (the PCMM) specification: Residual PCMM: (778.0 g). Yield: 77.0%, Purity: 92.61% with CTC-0.07% (by GC).

[0115] Step 2: In 400 g water, 44.60 g (48%) NaOH solution was charged and then cooled to 10-15° C. To the above solution, 81.38 g tetrahydrophthalimide was slowly added in 10-15 min span and further stirred for 45 min at same temperature clear solution was observed and then cooled to 0-2° C. to obtain reaction mass. Separately, 100.4 g PCMM solution obtained in step 1 was added to above reaction mass during addition precipitation was observed and stirred for 2.0 hrs at same temperature. In work up, toluene (323 g) was charged and reaction mass was heated to 75-80° C. under stirring for 30 min and cooled to 20-25° C., filtered and the washed with toluene (85 g) and hot water (98 g) two times to finally give an isolated dry solid of 133.4 g. Final sulfenyl phthalimide compound specification: Yield: 88.78%, Purity: 98.70% with 0.0092% CTC.

Example 2 Synthesis of 3a,4,7,7a-Tetrahydro-N-(Trichloromethanesulphenyl) Phthalimide

[0116] Step-I: In 323.6 g water, 188.8 g (30%) aqueous HCl solution and carbon disulfide (73.6 g) was charged at 5-10° C. and chlorine gas was purged for 22-24 hrs at the same temperature. After completion of reaction, layers were separated. chlorobenzene (48.4 gm) was added to organic mass and washed two times with 48.4 gm water. 192.0 g crude Perchloromethyl Mercaptan (PCMM) chlorobenzene solution was obtained. Distillation was performed of crude PCMM chlorobenzene solution on 3 feet packed column to remove low boiler and haloalkane impurity, carbon tetrachloride (CCl.sub.4) along with chlorobenzene under vacuum. The PCMM chlorobenzene solution thus obtained was further taken for step 2. Final sulfenyl compound (the PCMM) specification: Residual PCMM: (147.2 g). Yield: 72.0%, Purity: 88.10% with, CTC-0.06%.

[0117] Step 2: In 302.4 g water, 33.72 g (48%) NaOH solution was charged and then cooled to 10-15° C. To the above solution, 61.3 g tetrahydrophthalimide was slowly added in 10-15 min span and further stirred for 45 min at same temperature clear solution was observed and then cooled to 0-2° C. to obtain reaction mass. Separately, 79.8 g PCMM solution obtained in step 1 was added to above reaction mass during addition precipitation was observed and stirred for 2.0 hrs at same temperature. In work up, chlorobenzene (244 g) was charged and reaction mass was heated to 75-80° C. under stirring for 30 min and cooled to 20-25° C., filtered and the washed with chlorobenzene (64.2 g) and hot water (74.1 g) two times to finally give an isolated dry solid of 91.5 g. Final sulfenyl phthalimide compound specification: Yield: 80.54%, Purity: 97.80% with CTC-0.008%.

Example 3 Synthesis of 3a,4,7,7a-Tetrahydro-N-(Trichloromethanesulphenyl) Phthalimide

[0118] Step-I: In 323.6 g water, 188.8 g (30%) aqueous HCl solution and carbon disulfide (73.6 g) was charged at 5-10° C. and chlorine gas was purged for 22-24 hrs at the same temperature. After completion of reaction, layers were separated. Xylene (48.4 gm) was added to organic mass and washed two times with 48.4 gm water. 194.0 g crude Perchloromethyl Mercaptan (PCMM) xylene solution was obtained. Distillation was performed of crude PCMM xylene solution on 3 feet packed column to remove low boiler and haloalkane impurity, carbon tetrachloride (CCl.sub.4) along with xylene under vacuum. The PCMM xylene solution thus obtained was further taken for step 2. Final sulfenyl compound (the PCMM) specification: Residual PCMM: (143.0 g). Yield: 70.40%, Purity: 88.70% with CTC-0.07%.

[0119] Step 2: In 302.4 g water, 33.72 g (48%) NaOH solution was charged and then cooled to 10-15° C. To the above solution, 61.3 g tetrahydrophthalimide was slowly added in 10-15 min span and further stirred for 45 min at same temperature clear solution was observed and then cooled to 0-2° C. to obtain reaction mass. Separately, 79.3 g PCMM solution obtained in step-1 was added to above reaction mass during addition precipitation was observed and stirred for 2.0 hrs at same temperature. In work up, xylene (244 g) was charged and reaction mass was heated to 75-80° C. under stirring for 30 min and cooled to 20-25° C., filtered and the washed with xylene (64.2 g) and hot water (74.1 g) two times to finally give an isolated dry solid of 88.0 g. Final sulfenyl phthalimide compound specification: Yield: 77.46%, Purity: 97.71% with CTC 0.0084% .

Example 4 Synthesis of 3a,4,7,7a-Tetrahydro-N-(Trichloromethanesulphenyl) Phthalimide

[0120] Step-I: In 323.6 g water, 188.8 g (30%) aqueous HCl solution and carbon disulfide (73.6 g) was charged at 5-10° C. and chlorine gas was purged for 22-24 hrs at the same temperature. After completion of reaction, layers were separated. Ethyl benzene (48.4 gm) was added to organic mass and washed two times with 48.4 gm water. 190.0 g crude Perchloromethyl Mercaptan (PCMM) ethyl benzene solution was obtained. Distillation was performed of crude PCMM ethyl benzene solution on 3 feet packed column to remove low boiler and haloalkane impurity, carbon tetrachloride (CCl.sub.4) along with ethyl benzene under vacuum. The PCMM ethyl benzene solution thus obtained was further taken for step 2. Final sulfenyl compound (the PCMM) specification: Residual PCMM: (146.3 g). Yield: 71.80%, Purity: 88.40% w/w with CTC-0.06%.

[0121] Step 2: In 302.4 g water, 33.72 g (48%) NaOH solution was charged and then cooled to 10-15° C. To the above solution, 61.3 g tetrahydrophthalimide was slowly added in 10-15 min span and further stirred for 45 min at same temperature clear solution was observed and then cooled to 0-2° C. to obtain reaction mass. Separately, 79.60 g PCMM solution obtained in step 1 was added to above reaction mass during addition precipitation was observed and stirred for 2.0 hrs at same temperature. In work up, ethyl benzene (244 g) was charged and reaction mass was heated to 75-80° C. under stirring for 30 min and cooled to 20-25° C., filtered and the washed with ethyl benzene (64.2 g) and hot water (74.1 g) two times to finally give an isolated dry solid of 95.0 g. Final sulfenyl phthalimide compound specification: Yield: 83.6%, Purity: 98.61% with CTC-0.0088%.

Example 5: Synthesis of Perchloromethylmercaptan (PCMM)

[0122] In 1664 g water, 974 g (30%) aqueous HCl solution and 380 g carbon disulfide was charged at 5-10° C. and chlorine gas was purged for 22-24 hrs at same temperature. After completion of reaction, layers were separated, organic mass was collected and toluene (210 gm) was added and further organic layer was washed two times with 250 gm water. 905 g crude Perchloromethyl Mercaptan (PCMM) toluene solution was obtained. Distillation was performed of crude PCMM toluene solution on 3 feet packed column to remove low boiler and haloalkane impurity, carbon tetrachloride (CCl.sub.4) along with toluene under vacuum. Final sulfenyl compound (the PCMM) specification: Residual PCMM: (778.0 g). Yield: 77.0%, Purity: 92.61% with CTC-0.07%.

Example 6: Synthesis of N-(Trichloromethanesulphenyl)phthalimide

[0123] Step 1: In 1664 g water, 974 g (30%) aqueous HCl solution and 380 g carbon disulfide was charged at 5-10° C. and chlorine gas was purged for 22-24 hrs at same temperature. After completion of reaction, layers were separated, organic mass was collected and toluene (210 gm) was added and further organic layer was washed two times with 250 gm water. 905 g crude Perchloromethyl Mercaptan (PCMM) toluene solution was obtained. Distillation was performed of crude PCMM toluene solution on 3 feet packed column to remove low boiler and haloalkane impurity, carbon tetrachloride (CCl.sub.4) along with toluene under vacuum. The PCMM toluene solution thus obtained was further taken for step 2. Final sulfenyl compound (the PCMM) specification: Residual PCMM: (778.0 g). Yield: 77.0%, Purity: 92.61% with CTC-0.07%.

[0124] Step 2: In 200 g water, 24 g (48%) NaOH solution was charged and then cooled to 10-15° C. To the above solution, 40.3 g phthalimide was slowly added in 10-15 min span and further stirred for 45 min at same temperature clear solution was observed and then cooled to 0-2° C. to obtain reaction mass. Separately, 53.98 g PCMM solution obtained in step 1 was added to reaction mass during addition precipitation was observed and stir it for 2.0 hrs at same temperature. In work up, toluene (174 g) was charged and reaction mass was heated to 75-80° C. under stirring for 30 min and cooled to 20-25° C., filtered and the washed with toluene (45.6 g) and hot water (52.6 g) two times to finally give an isolated dry solid of 55.8 g. Final sulfenyl phthalimide compound specification: Yield: 70%, Purity: 96.0% .

[0125] Therefore, the fungicidal sulfenyl phthalimide compound substantially free from haloalkane impurity was successfully prepared using a process according to the present invention. Treatment of crude sulfenyl compound with aromatic hydrocarbon results into sulfenyl compound with lesser haloalkane impurity and the resulting sulfenyl compound further utilized for synthesizing sulfenyl phthalimide compound substantially free from haloalkane impurity. It is to be understood that the invention is not to be limited to the details of the above embodiments, which are described by way of example only.