ChemSpec India 2017

1. TECHNOLOGY OF CROP PROTECTION CHEMICALS
Dr. Surendra Bhatia
Sapec Agro SA

2. Classifications of Crop Protection Chemicals
INSECTICIDES HERBICIDES FUNGICIDES
Tefluthrin Rimsulfuron Fosetyl al
Bifenthrin Nicosulfuron Epoxiconazole
Lambda cyhalothrin Sulcotrione Cyproconazole
Imidacloprid Mesotrione Difenconazole
Acetamiprid Tembotrione Metalaxyl M
Thiacloprid Diclofop methyl Iprodione
Temephos Clodinafop propaargyl
Indoxacarb Dimethenamid P
s-Metolachlor
Imazapic
Imazethapyr

3. Chemistry Classifications
• Synthetic Pyrethroids
• Indanone Insecticides
• Organophosphorus compounds
• Neonicotinides
• Cyclohexandione
• Triazoles
• Chiral hydrogenations

4. SYNTHETIC PYRETHROIDS

5. SYNTHETIC PYRETHROIDS: KEY INTERMEDIATES
• LAMBDA CYHALOTHRIN
2-hydroxy-2-(3-phenoxyphenyl)acetonitrile
• TEFLUTHRIN
(2,3,5,6-tetrafluoro-4- methylphenyl)methanol
• BIFENTHRIN
(2-methyl-[1,1'-biphenyl]-3-yl)methanol
(E)-3-(2-chloro-3,3,3-trifluoroprop-1-
en-1-yl)-2,2-dimethylcyclopropane-1-
carbonyl chloride

6. Modifying proven technologies

7. NEONICOTINOIDS
• N-nitrosoamine destruction is the key to success

8. NEONICOTINOIDS: KEY INTERMEDIATES
• THIACLOPRID
• (E)-N-(thiazolidin-2-ylidene)cyanamide
* ACETAMIPRID
(E)-N'-cyano-N-methylacetimidamide
• IMIDACLOPRID

9. ORGANOPHOSPHOROUS COMPOUNDS
• Although old products , their demands are increasing if produced with High Purity

10. ORGANOPHOSPHOROUS COMPOUNDS: KEY INTERMEDIATES
• FOSETYL Al
diethyl phosphonate
• TEMEPHOS
O,O-dimethyl phosphorochloridothioate
• TEMEPHOS
4,4'-thiodiphenol

11. INDOXACARB
• An important insecticide from DuPont

12. INDOXACARB INTERMEDIATES
• methyl 5-chloro-1-oxo-2,3-
dihydro-1H-indene-2-carboxylate
• methyl 5-chloro-2-hydroxy-1-oxo-2,3-
dihydro-1H-indene-2-carboxylate

13. INDOXACARB INTERMEDIATE
• There are alternatives to this process. One can do carbamoylation at
the end

14. SULFONYL UREAS

15. TECHNOLOGY SHIFT IN SULFONYL UREAS – FROM ISOCYANATES TO
CHLOROFORMATES
• The use of Phosgene and butylisocyanate is replaced by comparately safer intermediates like
chloroformates2-Amino-4,6-dimethoxypyrimidine can be easily synthesized or procured

16. KEY INTERMEDIATES OF SULFONYL UREAS
• Nicosulfuron
• 2-chloronicotinic acid4,6-dimethoxypyrimidin-
2-amine
• Rimsulfuron
• 2-chloropyridin-3-amine

17. TRIKETONE HERBICIDES

18. TRIKETONE HERBICIDES: KEY INTERMEDIATES
• SULCOTRIONE
2-chloro-4-(methylsulfonyl)benzoyl chloride
• MESOTRIONE
4-(methylsulfonyl)-2-nitrobenzoyl chloride
• TEMBOTRIONE
2-chloro-4-(methylsulfonyl)-3-((2,2,2-trifluoro
ethoxy)methyl)benzoyl chloride
cyclohexane-1,3-dione

19. FOP HERBICIDES
• Dicofop Me is an important compound in FOP family. The technology of the preparation of Phenoxyphenol
holds the key.

20. FOP HERBICIDES: KEY INTERMEDIATES
• DICLOFOP METHYL
4-(2,4-dichlorophenoxy)phenol
• CLODINAFOP PROPARGYL
• 2-(4-((5-chloro-3-fluoropyridin-2-yl)oxy)phenoxy)
propanoic acid

21. IMIDAZOLINONE
• These are the herbicides from Dow

22. IMIDAZOLINONE: KEY INTERMEDIATES
• IMAZAPIC
dimethyl 5-methylpyridine-
2,3-dicarboxylate
• COMMON
INTERMEDIATE
2-amino-2,3-
dimethylbutanamide
• IMAZETHAPYR
diethyl 5-ethylpyridine-2,3-
dicarboxylate

23. AMIDE HERBICIDES
• Chiral reduction is the key aspect of process development of these technologies

24. AMIDE HERBICIDES: KEY INTERMEDIATES
• DIMETHENAMID P
2,4-dimethylthiophen-3-amine
• S-METOLACHLOR
2-ethyl-6-methylaniline
1-methoxypropan-2-one

25. KEY TECHNOLOGY
• Preparation of Imine
• Chiral hydrogenation
• Homogeneous catalysis

26. TRIAZOLE FUNGICIDES

27. TRIAZOLE FUNGICIDES: KEY INTERMEDIATES
• CYPROCONAZOLE
2-(4-chlorophenyl)-2-(1-
cyclopropylethyl)oxirane
• EPOXICONAZOLE
• 2-(bromomethyl)-3-(2-
chlorophenyl)-2-(4-
fluorophenyl)oxirane
• DIFENOCONAZOLE
2-(bromomethyl)-2-(2-chloro-4-
(4-chlorophenoxy)phenyl)-4-
methyl-1,3-dioxolane

28. ANILIDE FUNGICIDES
• It is becoming an important compound replacing metalalaxyl

29. ANILIDE FUNGICIDES: KEY INTERMEDIATES
methyl (2,6-dimethylphenyl)alaninate 2-methoxyacetyl chloride

30. IMIDAZOLE FUNGICIDES
• Preparation of 3,5-Dichloroaniline holds the key

31. IMIDAZOLE FUNGICIDES: KEY INTERMEDIATES
• 3-(3,5-dichlorophenyl)imidazolidine-2,4-dione
• 2-isocyanatopropane

32. Technology Focus
• Move from Batch Processes to Continuous/Flow Chemistry
• Backward Integration up to Basic Building Blocks
• Green Chemistry
• Recycle/Recovery of solvents
• Zero Discharge