Annexure-I List of Products with production capacity
Sr. Common Name IUPAC Name Quantity (MTPA) No. EC Production Proposed Total Production quantity change quantity after change in product mix and as per the valid CTO 1 CPFK 1-cyclopropy-2(2fluorophenyl) ethanone 105 55 -55 00 2 CNZ Cyanazine 120 70 -70 00 3 AE 473 (2-{2-chloro-4-mesyl-3-[(RS)]-tetrahydro-2- 99 50 -50 00 furylmethoxymethyl} benzoyl)-cyclohexane- 1, 3-Dione) 4 IBCZ (4-chlorophenyl)methyl N-(2,4- 70.2 40.2 -40.2 00 dichlorophenyl)-1H-1,2,4-triazole-1- ethanimidothioate 5 MY-71 3-[1-(3,5-dichlorophenyl)-1-methylethyl]-6- 99 10 -10 00 methyl-5-phenyl-2,3-dihydro-4H-1,3-oxazin- 4-one 6 MY-100 3-[1-(3,5-dichlorophenyl)-1-methylethyl]- 90 25 -25 00 3,4-dihydro-6-methyl-5-phenyl-2H-1,3- oxazin-4-one 7 PFD N-{3-isobutyl-4-[1,2,2,2-tetrafluoro-1- 360 100 -100 00 (trifluoromethyl) ethyl]phenyl}-1,3,5- trimethyl pyrazole -4- carboxylic amide 8 TLF Tolfenpyrad 225 225 -225 00 9 TBFN 4-chloro-N-[[4-(1,1- 120 120 -120 00 dimethylethyl)phenyl]methyl]-3-ethyl-1- methyl-1H-pyrazole-5-carboxamide 10 PYCL 1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5- 105 150 -150 00 a]pyridin-2-yl)-5-[methyl(prop-2- ynyl)amino]pyrazole-4-carbonitrile 11 LAKE PALACE 3-[[(2,5-dichloro-4- 240 240 -240 00 ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro- 5,5-dimethylisoxazole 12 OCTOPUSSY 3-[[[5-(difluoromethoxy)-1-methyl-3- 660 1500 -1500 00 (trifluoromethyl)-1H-pyrazol-4- yl]methyl]sulfonyl]-4,5-dihydro-5,5- dimethylisoxazole 13 2C6SMT 3-Chloro-2-Methylthioanisole 540 140 -140 00 14 DMI 2,6-dimethylindanone 180 600 -600 00 15 ORST Orysastrobin 420 170 -170 00 16 PCM N-(2 Chloro-4 Fluoro-5-((ethoxy carbonyl)- 420 1000 -1000 00 amino)-benzoyl)-N-iso-propyl-N-methyl- sulfamid 17 ACH 3-(difluoro methyl)-1-methyl-1H-pyrazole-4- 360 200 -200 00 carboxylic acid 18 Star-1 Pethoxamid Technical 720 48 -48 00 19 CFPA 3,4-dichloro-5-fluorobiphenyl-2-amine 300 300 -300 00 20 AMB 3,4,5-Trifluoro-aminobiphenyl 300 100 -100 00 21 PRZ Difluoro Methyl-N-Methyl Pyrazolic acid 480 300 -300 00 22 DCPA 1,3-dimethyl-5-chloro-4-pyrazolylcarboxylic 360 360 -360 00 acid chloride 23 CMTB 2-chloro-4-(methylsulfonyl)-3-[(2,2,2- 300 300 -300 00 trifluoroethoxy) methyl] benzoic acid 24 ZXMD Zoxamide 360 100 -100 00 25 AZST methyl (E)-2-{2-[6-(2-cyanophenoxy) 360 100 -100 00 pyrimidin-4-yloxy]phenyl}-3- methoxyacrylate
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26 CDMB 4-chloro 2,6-dimethyl-bromo benzene. 300 300 -300 00 27 PMT Phosmet 900 100 -100 00 28 Flub/SOD N-(2-Methylsulfinyl-1,1-dimethyl-ethyl)-N'-{ 0 300 -300 00 2-methyl-4-[1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl]phenyl} phthalamide 29 CCITM Disodium cyanocarbonodithioimidate 0 140 -140 00 30 IBA 3-(2-Methylpropyl)aniline 0 50 -50 00 31 FNZQ 4-tert-Butylphenethyl quinazolin-4-yl ether 0 100 -100 00 32 DMAI (1R,2S) and (1S,2S)-2,6-dimethyl-2,3- 0 200 -200 00 dihydro-1H-inden-1-amine 33 Tembutrion 2-({2-chloro-4-(methylsulfonyl)-3-[(2,2,2- 0 300 -300 00 trifluoroethoxy) methyl] phenyl}carbonyl)cyclohexane-1,3-dione 34 CCMP 2-Chloro-5-(chloromethyl)pyridine 0 300 -300 00 35 HFMOP 1,1,1,3,3,3-hexafluoro-2-methoxypropane 0 300 -300 00 36 MDO 2,2-Dimethyl-4-methylidene-1,3-dioxolane 0 100 -100 00 37 FMTQ 2-Ethyl-3,7-dimethyl-6-(4-(trifluoro 0 100 -100 00 methoxy)phenoxy)quinolin-4-yl methyl Insecticides and Intermediates -- 00 4800 4800 1 Amino Triazines a THM Bis (1,2,3 - Trithiacyclohexyl Dimethyl Ammonium) Oxalate 2 Diamides a Flub 3-Iodo-N2-(2-Methyl-1-(Methyl sulfonyl) Propan-2-yl)-N1-(2-Methyl-4- (Perfluoropropan-2-yl) phenyl) Phthalamide b SOD N2-(2-Methyl-1-(Methylsulfinyl)propan-2- yl)-N1-(2-Methyl- 4 - (perfluoropropan-2-yl) phenyl) phthalamide c MMTPA/SAA 2-Methyl 1-Methylthio-2-Propanamine 3 Hydazinopyridine a CHDP 3-Chloro-2-Hydrazino Pyridine 4 Nicotinamides a TFNA 2,6-Dichloro-4-(Trifluromethyl) pyridine-3- Carbonitrile 5 Nitroguanidines a BNHT 5-Benzyl-1-Methyl, 2-Nitro 2 imino- tetrahydro 1, 3, 5-trizan. b AETF 3-Amino methyl Tetrahydrofuran 6 Organophosphorus Insecticide a MTN 3-(Dimethoxy Phosphinothioyl sulfanyl methyl) -5-Methoxy-1,3,4-thiadiazol-2-one 7 Phenyl organo thiophosphate a PTF (RS)-(O-2,4-Dichlorophenyl O-Ethyl S-Propyl Phosphorodithioate) 8 Phthalimides a PMT Phosmet 9 Pyrazole-diamides a Q4039 3-Methyl Antranilic Acid b YB449 3-Methyl-2-Nitrobenzoic acid c DPX 2-Amino-5-Chloro-N,3-Dimethyl Benzamide d BPCA 3-Bromo-1-(3-Chloropyridin-2-yl)-1H- pyrazole-5-Carboxylic Acid 10 Quinazoline a FNZQ 3-[2-[4-(1,1-Dimethylethyl) phenyl] ethoxy] Quinazoline 11 Quinolinyl carbonate a FMTQ 2-Ethyl-3,7-Dimethyl-6-[4- (trifluoromethoxy) phenoxy]-4-Quinolyl Methyl Carbonate 12 Thiazolidines a CCITM Dimethyl Cyano Dithioimido Carbonate b CCMP 2-Chloro-5-Chloromethyl Pyridine
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Herbicides and Intermediates -- 00 5650 5650 1 Alkylazines a DMI 2,6-Dimethylindanone b DMAI 2,6-Dimethyl-2,3-Dihydro-1H-inden-1-amine 2 Amide-triazolones a IAT 3H-1,2,4-Triazol-3-one, 4-amino-2,4- dihydro-5-(1-methylethyl)- 3 Aryloxyphenoxy propionates a FPES Ethyl(2R)-2-{4-[6-chloro-1,3-benzoxazol-2- yl)oxy] phenoxy} propanoate 4 Benzoyl cyclohexanediones a AE 473 (2-{2-chloro-4-mesyl-3-[(RS)]-tetrahydro-2- furylmethoxymethyl} benzoyl)-cyclohexane- 1, 3-Dione) b Tembutrion 2-{2-chloro-4-(methylsulfonyl)-3-[(2,2,2- trifluoroethoxy)methyl]benzoyl}cyclohexane- 1,3-dione c 747 Either 2-Chloro-4-(methyl sulfonyl)-3-[(2, 2, 2- trifluoroethoxy) methyl] Benzoic acid d 2C6SMT 3-Chloro-2-Methylthioanisole 5 Furanones a FLURT 5-(Methylamino)-2-Phenyl-4-[3- (Trifluoromethyl) phenyl] furan-3(2H)-one 6 Intermediate of Herbicide a MTAA Methyl (methylthio) Acetate 7 Active nitrile Herbicide a PYCL 1-(3-Chloro-4,5,6,7-tetra hydropyrazolo [1,5-a] pyridin-2-yl)-5-[methyl (prop-2- ynyl)amino] pyrazole-4-carbonitrile 8 Oxazinones a MY-100 3-[1-(3,5-dichlorophenyl)-1-methylethyl]- 3,4-dihydro-6-methyl-5-phenyl-2H-1,3- oxazin-4-one 9 Oxazoles a Lake Palace 3-[[(2,5-dichloro-4-ethoxyphenyl) methyl] sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole 10 Oxazolidinediones a KPP Pantoxazone 11 Phosphinates a MPBS Methyldichlorophosphine 12 Pyrimidinediones a PCM N-(2 Chloro-4 Fluoro-5-((ethoxy carbonyl)- amino)-benzoyl)-N-iso-propyl-N-methyl- sulfamid b EATB Ethyl 3-amino-4,4,4-trifluorobut-2-enoate 13 Pyrimidinyloxybenzoic acid a Bispyribac sodium 2,6-bis(4,6-dimethoxypyrimidin-2- yloxy)benzoic acid 14 Pyrimidinylsulfonylurea a FRSF N,N-Dimethyl-2-[ N-[ N-(4,6-dimethoxy pyrimidin-2-yl)-Amino carbonyl] Amino sulfonyl]-4-(N-formylamino) benzamide, sodium salt b ESPS 3-ethylsulfonyl-2-pyridine sulfonamide 15 Sulfonylurea a AMSB(Mesylamide) Methyl 2-Amino-4-{[(methyl sulfonyl)amino] methyl} benzoate b OTMA 2-(Trifluoro Methoxy) Aniline 16 Triazines a CNZ Cyanazine 17 Triazopyrimidine sulfonamides
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a DTPBS N-(5,8-Dimethoxy [1,2,4] Triazolo [1,5-c] pyrimidine-2-yl)-2-Fluoro-6-(Trifluoro Methyl) Benzene Sulfonamide
Fungicides and intermediates -- 00 3550 3550 1 Active amide Fungicides a SSF-126/OXIME (2E)-2-(methoxyimino)-N-Methyl-2-(2- Phenoxy Phenyl) Acetamide b TRFRN N,N'-[1,4-Piperazinediyl-bis(2,2,2-Trichloro Ethylidene)]-Bis-[Formamide] c FNXL N-(1-Cyano-1,2-Dimethylpropyl)-2-(2,4— Dichlorophenoxy) Propanamide d MIPD (1E)-1-(2,5,5-Trimethyl-1,3-dioxan-2-yl) Propane -1,2-dione 1-(O-Methyloxime) e ORST Orysastrobin 2 Benzamides a ZXMD (RS)-3,5-Dichloro-N-(3-Chloro-1-Ethyl-1- Methyl-2-Oxopropyl)-p-Toluamide 3 Carboxamides a AMB 3,4,5-Trifluoro-Amino biphenyl 4 Organophosphates a KTZ(Kitazin) S-benzyl O,O-Diisopropyl Phosphorothioate 5 Pyridine Fungicides a CTPE 2-[3-Chloro-5-(Trifluoro methyl) Pyridin-2- yl] Ethanamine 6 Pyrimidines a AZST Methyl (E)-2-{2-[6-(2-Cyanophenoxy) pyrimidin-4-yloxy] phenyl}-3-Methoxy acrylate 7 Quinoxalines a CMTH 4-(Methoxy-6-(trifluoro methyl)-1,3,5- triazin-2-amine 8 Triazoles a IPCZ (1RS, 2SR, 5RS; 1RS, 2SR, 5SR)-2-(4- Chlorobenzyl)-5-Isopropyl-1-(1H-1,2,4- triazol-1-ylmethyl) Cyclopentanol b FTL 1-(2-Fluorophenyl)-1-(4-Fluorophenyl)-2-(1, 2, 4-Triazol-1-yl) Ethanol c FOX 2-(2-Fluorophenyl)-2-(4-Fluoro phenyl) Oxirane d IBCZ (4-Chlorophenyl) Methyl N-(2,4- Dichlorophenyl)-1H-1,2,4-Triazole-1- Ethanimidothioate
Fine Chemicals -- 00 7500 7500 1 Substituted Anthraanilic acid a ACBM 2-Amino-3-Chlorobenzoic Acid Methyl Ester 2 Substituted 1,2,4-Triazole a AMT 5-Amino-1,2,4-Triazole-3-thiol 3 Substituted tetrahydo pyran a ATHP 1-(Tetrahydropyran-4-yl) Ethanone 4 Dimethyl halo substituted benzene a CDMA 4-Chloro-2,6-Dimethyl Aniline b CDMB 4-Chloro 2,6-Dimethyl-Bromo benzene. 5 Substituted cyclopropyl ethanone a CPFK 1-Cyclopropy-2(2 Fluorophenyl) Ethanone 6 Substituted alkyl diamine a DAEEA N,N'-Bis(2-Hydroxyethyl) Ethylene Diamine 7 Substituted dihalo pyridine a DCTFP 2,3-Dichloro-5-(Trichloromethyl) Pyridine 8 Subsituted dimethyl dioxane methanol a DHD 2, 2-Dimethyl-5-Hydroxymethyl-1, 3- Dioxane
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9 Substituted Butanone a DMB 4,4-Dimethoxy-2-Butanone 10 Substituted Butanoic acid a EMBA 2-Ethyl-2-Methyl Butanoic acid 11 Substituted Hydrazine a MMH Mono Methyl Hydrazine b UDMH 1,1,-Dimethyl Hydrazine C SDMH 1,2-Dimethyl Hydrazine 12 Substituted Phenothiazine a 10-H Phenotiazine 10-H Phenotiazine 13 Substituted diphenyl ether a Metaphenoxy 3-Phenoxy Benzaldehyde benzaldehyde
Pyrazoles -- 00 5500 5500 1 n-alkyl 3,4,5 sustituted pyrazoles a PFD N-{3-Isobutyl-4-[1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl}-1,3,5- Trimethyl Pyrazole -4- Carboxylic Amide b TBFN 4-Chloro-N-[[4-(1,1-Dimethylethyl) Phenyl] Methyl]-3-Ethyl-1-Methyl-1H-Pyrazole-5- Carboxamide c TLF Tolfenpyrad d IBA 3-Isobutylanoline e OCTOPUSSY 3-[[[5-(Difluoro methoxy)-1-methyl-3- (Trifluoromethyl)-1H-pyrazol-4-yl] methyl] sulfonyl]-4,5-Dihydro-5,5-Dimethyl isoxazole f MY-71 3-[1-(3,5-Dichlorophenyl)-1-Methylethyl]- 3,4-Dihydro-6-Methyl-5-Phenyl-2H-1,3- oxazin-4-one g MTP 1-Methyl-3-(Trifluro methyl)1H-Pyrazol-5-ol h DCPA 1,3-Dimethyl-5-Chloro-4-Pyrazolyl Carboxylic Acid Chloride i CFPA 3,4-Dichloro-5-Fluoro Biphenyl-2-Amine j ACH 3-(Difluoro Methyl)-1-Methyl-1H-Pyrazole-4- Carboxylic Acid k BDB 4-Bromo- 1,2-Dichloro Benzene l PRZ Difluoro Methyl-N-Methyl Pyrazolic acid
Fluorospeciality products -- 00 2000 2000 1 Fluoro substituted alkyl amine a DFEA 2,2-Difluoro Ethylamine
Pharma intermediates -- 00 1000 1000 1 Substituted triazole carboxylate a EMTC Ethyl-4-Methyl-1,3-Thiazole-5-Carboxylate
Specialty Chemicals -- 00 1000 1000 1 Substituted cyclohexane carboxylate a ETMD Methyl cis-1-[2-(2,5-Dimethyl phenyl)-Acetyl amino]-4-Methoxy-Cyclohexane Carboxylate 2 Hepta Fluoro Alkane a HFMOP 1,1,1,3,3,3-Hexafluoro Isopropyl Methyl Ether 3 Substituted 1,3-dioxalane a MDO 2,2-Dimethyl-4-Methylene-1,3-Dioxalane 4 Substituted Isobutyrate a CMIBA Chloromethyl 2-Methyl Propanoate 5 Substitued plenyl ether a CMTB 2-Chloro-4-(Methyl sulfonyl)-3-[(2,2,2- trifluoro ethoxy) methyl] Benzoic Acid
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Performance Chemicals -- 00 13000 13000 1 Substituted phenyl morpholoine Ketone a PCBM 1-(4-Chlorophenyl)-2-methyl-2-(morpholin- 4-yl)propan-1-one 2 Catecol mixed salt a Negolyte Titanium Biscatecholate Monopyrogallate Sodium Potassium Salt
New R&D product for Pilot scale -- 00 240 240 Total 8593.2 8593.2 35646.8 44240
List of by products Sr. List of By- Quantity (MTPA) No. products EC Production Proposed Total Production quantity after change quantity change in product mix and as per the valid CTO 1 27% NaSH 444 49.25 950.75 1000 2 30 % HCl 8928 9090.1 2909.9 12000 3 Ammonia Solution 264 613.05 1000 386.95 15% 4 SMM 192 45.82 -45.82 00 5 H2SO4 0 85.0 215 300 6 Distill Solvent 0 90.0 6810 6900 7 Sodium Propionate 0 2402.2 -2.2 2400 8 NaBr/MgBr 5820 999.65 -999.65 00 9 Acetic Acid 0 300.0 900 1200 10 Spent Catalyst 0 100.20 -100.2 00 11 Orthocresol 0 0 300 300 12 Propionic Acid 0 0 900 900 13 HBr 0 0 1000 1000 14 Sodium hypochloride 0 0 900 900 solution 15 AlCl3 0 1872.8 427.2 2300 16 Ammonium Chloride 0 0 500 500 Total 15648 15648.07 14551.93 30700
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List of Raw Materials
Sr. List of Raw Materials Total No. after Expansion Quantity (MT/MT) Insecticides and intermediates 1. THM Monosultap 1.48 Xylene 0.56 Sodium hydroxide 0.78 Sodium Sulfide 0.59 Hydrogen Peroxide 0.04 Oxalic acid Dihydrate 0.47 2. Flub Sodium Bicarbonate 0.31 Sodium hydroxide 0.11 Toluene 1.63 SAA 0.31 Phthaloyl dichloride (PDC) 0.50 Tert butyl methyl ether 0.84 RFBr 0.69 O-Toluidine 0.33 Sodium hydrosulfite 0.43 N,N-Dimethyl acetamide 0.28 DIH 0.35 Dimethyl Acetamide 0.08 98% Formic acid 0.09 Conc. Sulfuric Acid 0.07 Hydrogen Peroxide 0.56 Caustic solution 0.58 3. SOD Sodium Bicarbonate 0.33 Sodium hydroxide 0.11 Toluene 1.73 SAA 0.33 Phthaloyl dichloride (PDC) 0.53 Tert butyl methyl ether 0.89 RFBr 0.73 O-Toluidine 0.35 Sodium hydrosulfite 0.45 N,N-Dimethyl acetamide 0.30 Hydrogen Peroxide 0.37 4. MMTPA 2-amino-2-methyl-1-propanol 0.75 Sulfuric Acid 0.82 Sodium Methyl Mercaptide 0.59 Caustic Soda 0.34 5. CHDP
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Hydrochloric acid 0.95 3-Amino Pyridine 1.08 Chlorine 0.98 Sodium Nitrate 0.58 Copper Chloride 0.08 Hydrazine hydrate 1.31 6. TFNA Potassium Hydroxide 0.81 2-Cyanoacetamide 1.11 Ethyl 3-oxo Trifluoro Acetoacetate 0.97 Methanol 0.50 Phosphoryl chloride 1.42 Sodium acetate 1.08 Sodium Hydroxide 0.46 Hydrochloric acid 0.16 7. BNHT 1-Phenylmethanamine 0.74 Methylnitro Guanidine 0.74 Formaldehyde 0.87 8. AETF 2-butene-1,4-diol 1.43 Carbon monoxide 0.02 Hydrogen 0.01 Sulfuric acid 0.03 Toluene 0.74 Raney Nickel 0.11 Ammonia 0.49 Ethyl Acetate 0.62 9. MTN Toluene 0.44 Phosphorous pentasulfide 0.73 Methanol 0.42 Tertbutyl Amonium bromide 0.01 Dry HCl gas 0.24 Ethylene Dichloride 1.27 M-Thiazone 0.50 Paraformaldehyde 0.12 Sulfuric acid 0.04 10. PTF Sulphur 0.13 Phosphorous trichloride 0.76 n-Propyl Mercaptane 0.30 Toluene 0.40 Methyl Ethyl Pyridine 1.78 Ethanol 0.22 2,4 Dichlorophenol 0.56 Sodium Hydroxide 0.15 11. PMT Methanol 0.30
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Phosphorous pentasulfide 0.54 Catalyst 0.00 23.5 % Caustic sol. 0.38 Phthalimide 0.62 37% formalin 0.52 Thionyl Chloride 1.04 Sodium Hydroxide 0.09 12. Q4039 Acetic Acid 1.98 2-Nitro-1,3-dimethylbenzene 1.26 Acetaldehyde 0.48 Oxygen 0.85 Methanol 1.82 Hydrogen Gas 0.04 13. YB449 Acetic Acid 0.36 2-Nitro-1,3-dimethylbenzene 1.20 Acetaldehyde 0.38 14. DPX Acetic Acid 5.20 Oxygen 0.09 2-Nitro-1,3-dimethylbenzene 3.35 Acetaldehyde 1.17 Caustic flakes 0.08 Methanol 5.40 Hydrogen Gas 0.04 Aq. Sodium Hydroxide 1.85 Potassium carbonate 1.00 Toluene 2.63 Ethyl chloroformate 0.80 Hydrochloric acid 2.35 Hydrogen Peroxide 0.57 Sodium sulfite 0.08 Methane sulpfonic acid 0.02 Ethyl acetate 0.97 Methylamine 0.23 15. BPCA 3 chloro-2-pyridinone hydrazone 0.46 Acetonitrile 3.02 Diethyl maleate 0.64 Hydrochloric acid 0.36 phosphorous oxy bromide 0.76 potassium per sulphate 0.52 Sodium Hydroxide 0.16 Sulphuric Acid 0.76 16. FNZQ Caustic Solution 1.64 4-Hydroxyquinazoline 0.58 Tert-butyl phenyl ethanol 1.00
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Thionyl Chloride 5.01 17. FMTQ 3-Pantanone 0.56 Aluminium trichloride 0.68 Chlorine gas 0.62 Dimethyl Acetamide 2.30 Hydrogen 0.03 Iron chloride 0.00 Isopropyl Alcohol 0.96 Methanol 0.19 Methyl chloroformate 0.24 Methylene Dichloride 0.43 Nitric Acid 0.36 Potassium carbonate 0.45 p-Toluyl chloride 0.46 Sodium hydroxide 0.20 Sulfolane 0.52 Sulphuric Acid 0.61 Tetra butyl ammonium bromide 0.04 Toluene 0.24 Trifluoro methoxy phenol 0.58 Xylene 0.49 18. CCITM 50% Aq. Cynamide 0.65 Carbondisulphide 0.75 Methylchloride 1.35 19. CCMP 3-Picoline 1.55 Azo Isobutyro nitrile 0.03 Benzoyl Chloride 0.69 Chlorine Gas 0.68 Hydrochloric acid 0.13 Hydrogen Peroxide 1.35 Methylene dichloride 0.74 Sodium Hydroxide 0.31 Sodium Tungstate 0.01 Sulphuric Acid 0.09 Triethyl Amine 0.99 Herbicides and Intermediate 20. DMI Propionic anhydride 1.81 Sodium Propionate 1.08 4-methyl benzaldehyde 1.27 Hydrogen 0.03 Caustic lye (30%) 0.35 Toluene 3.21 Phosphorous trichloride 0.30 21. DMAI Formamide 1.70
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Formic Acid 0.67 DMI 0.76 Hydrochloric acid 0.81 Caustic Soda 1.07 22. IAT Toluene 1.23 Iso Butyric Acid 0.73 Hydrazine Hydrate 0.44 Titatnium Dioxide 0.03 1,2-dichloro Ethane 0.79 Caustic Soda 0.67 Methyl Chloroformate 0.75 Hydrazine Hydrate 0.39 23. FPES Toluene 2.91 Ethyl(2R)-2-(4-hydroxy phenoxy) propanoate 0.61 Polyethylene Glycol 0.03 Potassium Carbonate 0.51 2,6-dichlorobenzene oxazole 0.57 24. AE-743 10% Sodium hypochlorite Sol. 4.00 30% Sodium Hydroxide 1.32 Xylene 1.26 AE-513 1.02 Thionyl Chloride 0.40 Acetonitrile 0.86 1,3 Cyclohexanedione 0.34 Triethyl Amine 0.64 Acetone cyanohydrin 0.03 5% Sodium Bicarbonate 0.30 35% HCl 0.88 Isopropanol 0.45 Caustic Flakes 0.08 25. TMBT Toluene 10.09 747 Ether 0.94 Thionyl chloride 1.00 1,3 Cyclohexanedione 0.32 Triethyl amine 0.69 Cyanohydrine 0.24 26. 747 Ether Ortho DiChloro Benzene 1.38 AE-014 1.17 NaOH Prills (97%) 0.42 Acetonitrile 0.54 Trifluoroethanol 1.02 HCl 30% 0.25 27. 2C6SMT 3-chloro-2-methyl aniline 0.82
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HCl (35%) 0.53 Sodium Nitrite 1.20 Sodium Carbonate 0.14 Ethylene Dichloride 0.78 Sodium Methyl Mercaptane 2.10 28. Flurt 3-trifluoromethylphenyl acetonitrile 2.00 Sodium Ethoxide 2.00 Ethyl Phenyl Acetate 1.55 Bromine 1.90 Glacial Acetic Acid 0.67 Methylamine 2.07 HCl 0.44 29. MTAA 32 % NaOH 0.07
Phosphoric Acid (H3PO4) 0.16 Tetra butyl ammonium bromide (TBAB) 0.02 Methyl chloro acetate 1.01 Sodium Methyl Mercaptane 0.25 Methylene dichloride 0.69 30. PYCL 1,1,7-trichloroheptene-3-one 0.76 Caustic Lye 0.56 Conc. HCl 0.25 Hydrazine Hydrate 1.06 Hydrogen Peroxide 0.63 Malononitrile 0.58 NaOH Soln 0.55 n-Butanol 0.56 Propargyl chloride 0.71 Tetra butyl ammonium bromide (TBAB) 0.14 Trimethylorthoformate 0.92 Zinc chloride 0.00 31. MY-100 Methyl phenyl Acetate 1.03 Ethyl acetate 0.54 Sodium Methanoate 1.20 HCl 0.19 3,5-dichlorobenzoyl Chloride 1.09 Chloromethane 1.46 Magnesium metal 0.12 Tetrahydrofuran 1.11 Acetonitrile 0.41 Sulphuric Acid 1.00 Sodium Hydroxide 2.25 Hexanol 2.13 Formaldehyde 1.10 Xylene 0.61 32. Lake Palace
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2,5 Dichloro Phenol 0.54 Sodium hydroxide 1.07 Diethyl Sulfate 0.61 Paraformaldehyde 0.59 HCl 0.29 BIO 4.31 Thiourea 0.30 Hydrogen Peroxide 0.76 Iso propyl alcohol 0.89 33. KPP 4 Fluorophenol 0.62 Chlorine 0.43 Caustic 0.59 Ethyl Chloroformate 0.74 Sulphuric Acid 0.52 Nitric Acid 0.58 Hydrogen Gas 0.06 Chloroformate 0.67 Alkyl Bromide 0.54 Alkyl Butaneoat 0.20 Toluene 0.73 34. MPBS Phosphorous trichloride 2.42 Aluminium Chloride 1.18 Methyl Chloride 0.47 Diethyl phthlate 1.56 Yellow Phosphorous 0.18 N-Butanol 0.90 NaOH 0.66 35 PCM 2-chloro 4 fluoro toluene 1.13 Chlorine gas 1.63 Oleum 0.74 Ethanol 0.51 N-isopropyl-N-methylamine 1.24 Ammonia 0.19 Thionyl Chloride 1.41 Methanol 0.32 Hydrogen 0.01 Ethyl chloro formate 1.10 Toluene 0.16 36. EATB Ethyl trifluoro acetate 0.93 Ethyl Acetate 0.82 Sodium Ethoxide 0.47 Acetic Acid 0.59 Ammonium Acetate 0.95 Sodium Bicarbonate 0.98 37. BPS
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Tetrahydrofuran 0.62 Sodium hydride 0.33 Dihydroxy benzoic acid 0.42 2-Methylsulfonyl-4,6-dimethoxypyrimidine 1.28 38. FRSF Tetrahydrofuran 0.83 2-Amino-4,6-dimethoxypyrimidine 0.45 Phenyl chloroformate 0.71 Acetonitrile 2.20 NSA 0.82 Potassium Carbonate 0.46 Hydrogen Gas 0.04 Sulphuric Acid 0.35 Formic Acid 0.56 Acetic anhydride 0.61 Acetone 0.33 Sodium Methanoate 0.47 39. ESPS 3-Aminopyridine 1.26 HCl 0.58 Ferric Chloride 0.08 Chlorine gas 0.83 Sodium Hydroxide 0.75 Sodium Bisulfite 0.70 Sodium Nitrite 0.53 Copper chloride 0.01 Caustic solution 0.26 Sodium Sulfite 1.68 Sodium bicarbonate 0.18 Ethyl Bromide 0.18 Potassium carbonate 0.23 Sodium hydro sulfide 0.51 Ammonia 0.26 40. AMSB Methyl 2-nitro 4-cyanobenzoate 1.05 Acetic Acid 0.97 Hydrogen Gas 0.04 Toluene 0.73 HCl Gas 0.11 Dimethyl Acetamide 0.80 Triethyl Amine 0.93 methane sulfonyl chloride 0.53 Methylene dichloride 1.40 41. OTMA Trifluoromethoxy benzene 1.52 Bromine 1.50 Fuming Nitric Acid 0.34 Sulphuric Acid 0.11 Methylene Dichloride 0.31
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Hydrogen Gas 0.08 42. CNZ 2-hydroxy-2-methylpropanenitrile 1.16 Ammonia 0.80 2,4,6-trichloro-1,3,5-triazine 1.88 Aq. Ethyl amine 0.47 43. DTPBS 4-amino-2,5-dimethoxypyrimidine 0.60 Ethoxy carbonylisothiocyanate 0.58 Toluene 0.44 Hydroxylamine 0.15 Methanol 0.26 2-fluoro-6-(trifluoromethyl) benzenesulfonyl chloride 0.74 44. SSF Molten Phenol 0.44 1,2-dichloro benzene 1.41 Potassium Hydroxide 0.58 Xylene 1.45 Magnesium Turnings 0.17 Ethyl Bromide 0.05 Di Butyl Oxalate 1.19 Methylamine 1.45 Hydroxyl amine sulphate 0.64 HCl 0.79 Potassium Carbonate 0.26 Dimethyl Sulphate 0.58 45. TRFRN Trichloroacetaldehyde 0.85 Formamide 0.25 Phosphorous Trichloride 0.90 Piperazine 1.09 46. FNXL Caustic solution 0.26 DCPPA 0.80 Toluene 0.90 Thionyl Chloride 0.43 ADMBN 0.45 Sodium bicarbonate 0.02 47%NaOH 0.04 47. MIPD Acetyl Acetone 0.54 Sulphuric Acid (50%) 0.53 Sodium Nitrite 0.94 NaCl 0.05 Potassium Carbonate 0.02 Dimethyl Sulphate 0.74 NPG 90% Neopentyl glycol 0.80 48. ORST MIPD-Ketal 0.92
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25% NaOH 0.50 Methoxy Amine hydrochloride 1.81 Hydroxylamoniumsulfate 2.22 Sodium Methylate 0.18 CLMO 0.78 Methylamine 0.30 49. ZXMD 3-Methyl-1-pentyne-3-ol 1.12 Phosphoryl chloride 1.94 Ammonia 0.76 Methyl-p-Toluate 1.09 Chlorine gas 0.61 HCl 0.32 NaOH 0.59 Thionyl Chloride 1.10 Methyl Isobutyl ketone 0.57 Silver nitrate 0.00 Trichloroisocyanuric acid (TClA) 0.41 50. AMB Magnesium turnings 0.15 Dry Tetrahydrofuran 0.66 AAA-BrTFB 1.21 Trimethoxyborane 0.66 10% HCl 0.22 47% Caustic lye 0.43 51. Kitazin SDTP 1.88 Toluene 0.25 Benzylchloride 0.44 52. CTPE 2,3 dichloro-5-trifluoromethyl)pyridine 1.10 N-Methyl-2-pyrrolidone 2.51 Potassium Hydroxide 0.64 Ethyl acetoacetate 0.69 HCl 1.47 Acetic anhydride 0.28 Acetic acid 0.43 Hydrogen 0.01 53. AZST 2(3H)-Benzofuranone 0.96 Trimethyl orthoformate 1.14 Acetic anhydride 1.42 Sodium methoxide 0.44 4,6-Dichloropyrimidine 1.15 2-cynophenol 0.48 Potessium carbonate 0.04 Dimethyl Formamide 0.50 54. CMTH Methyl trifluoroacetate 0.58
M/s. PI Industries Ltd. 16
Methanol 0.46 2-Cyanoguanidine 0.08 Sodium methoxide 0.36 55. IPCZ Dimethyl Adipate 1.96 Dimethyl Formamide 1.03 Isopropyl Bromide 1.47 N-methyl pyrrolidone 3.69 p-chlorobenzyl chloride 1.75 Potassium Iodide 0.15 Sodium Hydroxide 0.67 Sodium Methoxide 1.32 Sodium salt of 1,2,4-Triazole 0.77 Sodium tert-butoxide 0.44 TMSOB 1.60 Toluene 6.69 56. FTL Dimethyl Formamide 0.74 1,2,4-Triazole 0.46 Potassium carbonate 0.17 FOX 1.44 57. FOX 2-fluorobenzoyl Chloride 0.56 Fluorobenzene 0.30 Aluminium Chloride 0.43 dimethyl sulfoxide 0.81 dimethyl sulphate 0.87 Potassium hydroxide 0.08 DABCO 0.02 Toluene 0.41 58. IBCZ 2,4-dichloroaniline 0.90 Chloro Acetyl Chloride 0.86 Sodium Carbonate 0.43 Phosphorous pentachloride 0.60 Toluene 0.74 1-Chloro-4-(chloromethyl) benzene 1.01 Thiourea 0.55 HCl 0.35 NaOH 0.57 1,2,4-Triazole 0.58 Cyanomethane 0.34 59. ACBM 2,3 dichloro benzoic acid 1.06 Copper chloride 0.04 Ammonia 0.95 Hydrochloric acid 0.53 Methyl Isobutyl ketone 1.36 Dimethyl Sulphate 0.14
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Tertabutyl ammonium bromide 0.18 Potassium carbonate 0.04 60. AMT Aminoguanidine Bicarbonate 0.95 Ammonium Thiocynate 0.85 HCl 0.42 Caustic Soda 0.24 61. ATHP Bis dichloro diethylether 1.83 Dimethyl Formamide 3.61 Potassium carbonate 0.10 Potassium Iodide 0.22 Methyl Acetoacetate 1.00
H2SO4 (49%) 0.96 Sodium bicarbonate 0.05 Ethylene Dichloride 1.00 62. CDMA 2,6-Dimethylaniline 1.24 Ethylene Dichloride 1.58 Sulphuric Acid 1.11 Caustic 0.03 Chlorine Gas 0.24 63. CDMB Ethylene Dichloride 1.35 2,6-Dimethyl Aniline 0.99 Sulphuric Acid 0.98 Chlorine Gas 1.04 Hydrobromic Acid 1.89 Sodium Nitrite 0.60 64. CPFK Magnesium Turnings 0.38 2-Chloropropane 4.90 2-Fluoro Toluene 1.04 CPCM 0.46 HCl 0.51 65. DAEEA Ethylene Diamine 1.50 2-Chloro Ethanol 2.24 Sodium Carbonate 0.07 66. DCTFP Phosphorous Trichloride 1.55 Nicotinic Acid 0.35 Chlorine 1.32 Hydrogen fluoride 0.57 67. DHD Methanol 0.92 Paraformaldehyde 0.63 Diethylmalonate 1.52 Triethyl Ortho Formate 0.89
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Sodium Bisulphate 0.11 Acetone 0.71 Toluene 0.87 Dimethyl sulfoxide 1.38 Sodium chloride 1.10 Lithium aluminium hydride 0.44 Potassium hydroxide 0.02 68. DMB Methanol 3.40 Methyl formate 0.91 Acetone 0.64 Sodium Methoxide 0.35 Sulfuric Acid 0.12 69. EMBA Sodamide 0.97 Propionitrile 0.54 Ethyl Bromide 1.35 Tetrahydrofuran 1.73 Sulphuric Acid 1.11 70. MMH Chloroform 1.55 Hydrazine Hydrate 1.50 Caustic Lye 1.12 71. 10-H Phenothiazine Diphenylamine 0.90 Sulphur 0.34 72. MPB Benzaldehyde 0.14 Bromine 0.01 Chlorine 0.05 HCl solution 0.71 Formic Acid 0.01 Thio Solution 0.36 Soda solution 0.01 1,2-Ethanediol (MEG) 0.65 Cuprous chloride 0.01 Potassium Hydroxide 0.39 Phenol 0.60 Caustic Lye 0.19 Sulphuric acid 0.03 73. PFD Potassium Carbonate 0.07 Sodoium bisulphate 0.36 IBA 0.64 Ethyl Acetate 0.49 RFI 1.58 Sodium Methoxide 1.01 Zinc Chloride 0.34 N-methyl pyrrolidone 0.49
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TMC 0.65 Toluene 0.79 NaH in Paraffin 0.12 Isobutyryl chloride 0.33 74. TBFN 4-chloro-3-ethyl-1-methyl-1H-pyrazole-5carbonyl 1.80
Chloride 1-(4-tert-butylphenyl)methanamine 1.00 NaOH 0.40 75. TLF Methyl Ethyl Ketone 0.82 4-chloro benzonitrile 2.13 4-methyl Phenol 1.54 Diethyl Ethanedioate 1.63 Dimethyl Formamide 1.22 Dimethyl sulfate 1.41 HCl 0.40 Hydrazine Hydrate 1.17 Hydrogen 0.10 Methanol 1.11 Sodium Ethoxide 0.96 Sodium Hydroxide 3.35 Sodium Oxychloride 1.10 Thionyl Chloride 1.56 Toluene 0.82 76. IBA Mono chlorobenzene 0.70 Aluminium Chloride 1.80 Diethylene Gylcol 0.49 Fuming Nitric Acid 2.17 Hydrazine Hydrate 0.61 Hydrogen gas 0.13 Isobutyl chloride 1.58 Potassium Carbonate 0.08 Potassium Hydroxide 0.62 77. Octopussy Hydroxyl amine sulfate 0.42 Glyoxalic acid 0.75 NaOH sol 0.87
Na2CO3 sol. 0.13 Bromine 1.68 Sodium carbonate 0.69 Butyl acetate 1.14 Thiourea 0.27 HCl soln. 0.45 78. MY-71 1,3-dimethyl-5-pyrazolone 0.99 2,6- Dichloro Toluene 0.62
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Acetyl Chloride 1.18 Aluminium trichloride 1.13 Caustic 1.21 Hydrochloric Acid 0.45 Potassium carbonate 0.97 Sodium Hypochlorite 0.99 Thionyl chloride 2.76 Triethyl Amine 0.64 79. MTP Ethyl Acetate 1.92 Ethyl trifluoro acetate 1.03 Sodium Ethoxide 0.52 HCl 1.16 Acetic Acid 0.65 Monomethyl Hydrazine 0.90 80. DCPA DPMO 0.77 Dimethyl Formamide 0.99 Phosphoryl chloride 1.25 NaOH 1.50 Hydrogen Peroxide 0.78 HCl 0.22 Caustic solution 0.08 Toluene 1.00 Thionyl chloride 0.46 81. CFPA Magnesium turnings 0.16 Tetrahydrofuran 1.13 Bromo dichloro benzene 1.15 Tetramethyl benzidine 0.67 98% Sulphuric Acid 0.70 Toluene 0.51 2-bromo-4-fluoroaniline 0.93 Tripotassium phosphate 0.30 82. ACH Ethyl 4,4-difluoro-3-oxobutanoate 0.94 Trimethyl Orthoformate 1.73 Acetic Anhydride 0.55 O-Ethyl Acrylate 1.06 Mono Methyl Hydrazine 1.17 Acetone 0.41 HCl 0.04 Sodium hydroxide 0.09 Sulfuric acid 0.13 Thionyl chloride 0.49 83. BDB Ortho dichloro benzene 0.28 Aluminium trichloride 0.02 Bromine 1.13
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HCl 0.05 Sodium thiosulfate 0.09 84. PRZ Ethyl 4,4-difluoro-3-oxobutanoate 0.62 Acetic anhydride 1.36 Trimethylorthoformate 0.75 Acetone 0.45 Mono Methyl Hydrazine 0.79 Aq. HCl 0.07 Sodium Hydroxide 0.36 Sulfuric acid 0.19 85. DFEA N methyl pyrolidine 2.27 Ammonia 1.04 Difluoro chloro ethane 0.79 86. EMTC Ethyl acetoacetate 1.43 Sulfuryl Chloride 1.48 Tetrahydrofuran 2.28 Formamide 0.71 Phosphorous Pentasulphide 0.86 87. ETMD 2,5-Dimethylphenyl acetyl chloride 0.99 4-methoxy-cyclohexanone 0.77 Ammonia 1.80 Carbon Dioxide 0.17 HCl 0.22 Potassium Hydroxide 1.01 Chlorobenzene 1.70 Methanol 0.35 Sodium hydroxide 0.10 Sodium cyanide 0.32 Sulphuric Acid 0.04 88. HFMOP OIME 2.48 Tetramethyl ammonium chloride 0.03 Potassium Hydroxide 0.08 Sodium Bicarbonate 0.04 Sodium Hypochlorite 0.06 Dimethyl sulfate 0.93 Sodium Hydroxide 1.70 Dimethyl Formamide 0.72 KF 0.13 89. MDO Acetone 1.40 Epichlorohydrin 1.10 Tributyl amine 0.01 Tetra Ethylene Glycol 0.47
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Potassium hydroxide 0.05 90. CMIBA Isobutyryl Chloride 0.92 Paraformaldehyde 0.26 Anhydrous Zinc Chloride 0.02 91. CMTB AE-014 0.73 Dimethyl Formamide 1.46 Sodium hydride 0.29 Tri Fluoroethanol (TFE) 1.46 Toluene 2.08 NaOH 0.23 92. PCBM Chlorobenzene 1.99 Aluminum Chloride 1.77 Isobutyryl Chloride 1.25 1,2-Dichloro Ethane 0.71 Bromine 2.01 Sodium Bicarbonate 0.25 Sodium Methoxide 1.96 Morpholine 1.04 93. Negolyte Catechol 0.88 Toluene 1.97 Titanium chloride 0.52 Sodium hydroxide 0.22 Potassium Hydroxide 0.31 Ethylene diamine tetra acetic acid 0.03
M/s. PI Industries Ltd. 23
Annexure-II Manufacturing Process Insecticides and Intermediates 1. Bis (1, 2, 3-trithiacyclohexyl dimethyl lammonium) oxalate Manufacturing Process:
Step-1 Thiosultape or Monosultape treated with Na2S5H2O and NaOH forms TCB Step-2 TCB along with oxalic acid hydrate forms Thiocyclam Oxalate (THM)
Chemical reaction:
O O Na H C S 3 H C S S O 3 N .H O 2 + Na2S.5H NaOH N 2 Na SO . H3C S + S + 2 3 7 O H3C S S O OH Thiosultap/Monosultap TCB M.W.: 351.4 M.W.:181.4
H3C S HO O H C S N 3 HO O S . H H C + 2 N . 3 S 2H2O S O OH H3C + S O OH
TCB Oxalic Acid Hydrate Thiocycalm Oxalate M.W.:181.4 M.W.: 271.40 M.W.:126.0
Mass Balance: Mass Balance of THM Kg Kg Monosultap 737 196 Effluent to ETP Water 290 NaOH 80 Formation of Step-1 Na2S 177 Hydrogen Peroxide 32
Oxalic acid Dihydrate 233 78 Residue to Incinerator Formation of THM 275 Effluent to MEE 1000 THM
Total 1549 1549
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2. 3-Iodo-N2-(2-methyl-1-(methylsulfonyl)propan-2-yl)-N1-(2- methyl-4-(perfluoropropan-2-yl) phenyl) phthalamide Manufacturing Process:
Step-1 SAA and PDC react together along with Toluene, NaOH and NaHCO3 and forms ISM. O-Toludine and RFBr are agitated with Na2S2O4, NaHCO3 p-PTSA and
TBAB to form RFA. Side by side SOD and DIH reacts in presence of Pd(AcO)2 and DMAC forms ISO.
Step-2 ISO is oxidized with H2O2 along with HCOOH and H2SO4 forms FLUB and a wash with NaOH gives final Product FLUB. Chemical Reaction: ISM synthesis
CH3
CH CH N 3 3 1NaOH + H C COCl 3 1NaHCO 3 S 2NaCl + 2H O + CO + O CH3 + 2 2 H2N Toluene COCl S H3C O ISM SAA PDC
RFA Synthesis
NH2 NH2 Br TBME CH3 CH3 + 2NaOH + NaBr + 2SO2 + H2O + CO2 Na2S2O4 + NaHCO3 F3C F CF3
F C CF3 o - Touledine RFBr 3 F RFA
SOD intermediate synthesis
CF3 H3C O CH3 F CF3 H3C N CH3
NH S S O + CH3 NH Toluene/DMAC CH3 CH3 F O O NH2 H3C CF3 F3C ISM RFA SOD intermediate
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SOD Synthesis
O H C O H C 3 3 CH3 CH3 O NH NH S S H O H O NH + 2 NH 2 2 CH3 CH3 + F F O O H C H C 3 3 CF CF 3 3 F3C F3C
SOD SOD intermediate
ISO synthesis
O H3C O I O CH H3C 3 CH O O 3 I O NH CH3 2 S N NH CH3 2 S + HN NH + CH3 CH3 N NH CH3 DMAC CH3 O N F O H O I F O H C 3 H C CF 3 3 CF 3 F3C F3C
SOD DIH ISO
FLUB Synthesis
I O H3C I O CH H3C 3 CH O 3 O NH S HCOOH NH S CH3 2NaOH NH H2O2 O H O CH3 + NH 2 H2SO4 + F O F O H C 3 H C CF 3 3 CF F3C 3 F3C ISO Hydrogen peroxide FLUB
I O H3C CH3 O
NH S CH3 O CO + Na SO + H NH + 3H2O + 2 2 4 2
F O H3C CF 3 F3C FLUB
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Mass Balance: Mass balance of Flub Kg Kg Stage-I Water 133 8 Effluent to incinerator NaHCO3 21 1159 ISM NaOH 65 Formation of ISM Toluene 467 SAA 184 Phthaloyl dichloride (PDC) 298
Stage-II Rec. Tert butyl methyl TBME 839 822 ether RFBr 413 200 Effluent to ETP O-Toluidine 195 Formation of RFA 245 Residue to Incinerator Sodium bicarbonate 65 659 RFA Na2S2O4 43 DM Water 372
RFA (Stage-I) 659 695 Effluent to MEE ISM (Stage-II) 1159 832 Toluene recycled N,N-Dimethyl acetamide 283 889 Effluent to ETP Formation of SOD N,N-Dimethyl Toluene 849 272 acetamide recycled H2O2 206
DIH 209 309 Effluent to ETP DMAC 75 Formation of ISO 72 DMAC recovered DM Water 250
98% Formic acid 55 108 Effluent to ETP Conc. H2SO4 41 302 Residue to Incinerator Hydrogen Peroxide 132 Formation of Flub 1000 Flub DM Water 504 Caustic soln 58
Total 7572 7572
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3. N2-(2-Methyl-1-(Methylsulfinyl)propan-2-yl)-N1-(2-methyl-4 (perfluoropropan-2-yl) phenyl) phthalamide Manufacturing Process:
Step-1 SAA and PDC react together along with Toluene NaOH and NaHCO3 forms ISM. Step-2 ISM further treated with RFA and forms SOD-Intermediate.
Step-3 Oxidation of SOD Intermediate with H2O2 forms SOD.
Chemical Reaction: Step I CH3
CH CH N 3 3 1NaOH + H C COCl 3 1NaHCO 3 S 2NaCl + 2H O + CO + O CH3 + 2 2 H2N Toluene COCl S H3C O ISM SAA PDC
Step II NH2 NH2 Br TBME CH3 CH3 + 2NaOH + NaBr + 2SO2 + H2O + CO2 Na2S2O4 + NaHCO3 F3C F CF3
F C CF3 o - Touledine RFBr 3 F RFA
Step III CF3 H3C O CH3 F CF3 H3C N CH3
NH S S O + CH3 NH Toluene/DMAC CH3 CH3 F O O NH2 H3C CF3 F3C ISM RFA SOD intermediate
O H C O H C 3 3 CH3 CH3 O NH NH S S H O H O NH + 2 NH 2 2 CH3 CH3 + F F O O H C H C 3 3 CF CF 3 3 F3C F3C
SOD SOD intermediate
Mass Balance:
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Mass Balance of SOD Kg Kg Stage-I Water 141 9 Effluent to incinerator NaHCO3 22 1229 ISM NaOH 68 Formation of ISM Toluene 496 SAA 195 Phthaloyl dichloride (PDC) 316
Stage-II Rec. Tert butyl methyl TBME 890 872 ether RFBr 437 313 Effluent to ETP O-Toluidine 311 Formation of RFA 257 Residue to Incinerator Sodium bicarbonate 68 699 RFA to next step Na2S2O4 39 DM Water 613
RFA (Stage-II) 699 792 Effluent to MEE ISM (Stage-I) 1229 882 Toluene recycled N,N-Dimethyl acetamide 300 243 Effluent to ETP Formation of SOD N,N-Dimethyl acetamide Toluene 540 288 recycled H2O2 219 1000 SOD
Total 6584 6584
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4. 2-Methyl 1-Methylthio-2-Propanamine Manufacturing Process: Step-1 The AMP (2-amino-2-methyl-1-propanol) solution reacted with ~ 50% sulfuric acid to form intermediate (2-amino-2-methylpropyl hydrogen sulfate). Step-2 Intermediate is reacted with sodium methyl mercaptide solution in presence of caustic solution to form MMTPA. The reaction mass is subsequently worked-up to get crude MMTPA. Thereafter, crude MMTPA is fractionated to obtain final MMTPA Chemical Reaction:
Step I
H3C CH3 H3C CH3 OH OSO3 -
H2SO4 + H2O + + H2N H3N
2-amino-2-methyl-1 Sulfuric acid 2-amino-2-methylpropyl -propanol hydrogen sulfate (Ester)
Step II
H3C CH3 H3C CH3 OSO3 - SCH3 Na SO H O + CH3SNa + NaOH + 2 4 + 2 + H N H N 3 Sodium methyl 2
mercaptide 2-methyl-1-methylthio 2-amino-2-methylpropyl -2-propanamine hydrogen sulfate (Ester) (MMTPA) Mass Balance: Mass Balance of 2-Methyl 1-Methylthio-2-Propanamine/MMTPA/SAA Kg Kg 2-amino-2-methyl-1- 748 propanol Formation Step 1 Sulfuric Acid 330 151 Effluent to ETP
Sodium Methyl 588 Formation of 2-methyl 1- 1120 Effluent to MEE Mercaptide methylthio-2- Caustic Soda 34 225 Salt to Incinerator propanamine/MMTPA/SA Water 797 1000 MMTPA A
Total 2496 2496
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5. 3-chloro-2-hydrazinopyridine Manufacturing Process: Step-1 Chlorine gas along with AMP and hydrochloric acid gives CAMP
Step-2 CAMP is further reacted with NaNO2 with charging of HCl produce DCP Step –3 DCP is further reacted with Hydrazine mono hydrate to form final product 3-chloro-2-hydrazinopyridine (CHDP) Chemical Reaction: Step I
NH2 HCl NH2 + Cl Cl + HCl N N Cl
3-Aminopyridine Chlorine 2-Chloro-3-Aminopyridine gas (AMP) (CAMP)
Step II NH2 Cl NaNO 2 N (g) NaCl + 2 + + 2 + + 2 H2 N Cl N Cl
2-Chloro-3-Aminopyridine 2,3-Dichloropyridine (CAMP) (DCP)
Step III Cl Cl NH .NH H O H O HCl + 2 2 2 NH + 2 + N Cl N NH 2
2,3-dichloropyridine Hydrazine mono hydrate 3-chloro-2-hydrazinopyridine (DCP) (CHDP)
Mass Balance: Mass Balance of CHDP Kg Kg HCl 33 187 Effluent to Incinerator 3-Amino Pyridine 431 Formation of 251 Effluent to MEE Chlorine 390 Step 1 DM Water 453
HCl 12 686 Effluent to MEE Sodium Nitrate 231 Formation of 118 Residue to incinerator DM Water 348 Step 2 Copper Chloride 32
Hydrazine hydrate 524 312 Effluent to ETP Formation of DM Water 178 78 LOD to incinerator Step 3 1000 CHDP
Total 2633 2633
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6. 2, 6- dichloro-4-(trifluromethyl) pyridine-3-carbonitrile Manufacturing Process: Ethyl 4,4,4-trifluoroacetoacetate and Cyanoacetamide along with KOH and MeOH forms 2,4-dioxo-6-(trifluoromethyl)-1H-pyridine-3-carbonitrile. 2, 4- dioxo-6-(trifluoromethyl)-1H-pyridine-3-carbonitrile is further treated with POCl3 and Chlorine is added with benzene ring. Hydrogen gas is allowed to pass in the reaction vessel in presence of sodium acetate which removes the chlorine from benzene ring. And in the end sodium hydroxide and hydrochloric acid are added to form final product TFNA. Chemical Reaction: OH
O NH O O KOH F F CH CH OK H O O + N O + 3 2 + 2 F NH2 F F MeOH F C C N C
OH Cl POCl NH N HCl H3PO4 + F F + O H2O Cl F F F F N N C C
Cl N N H2 2 CH COOH + 2 NaCl F + 3 F Cl F F NaOAc F F N N C C
N NaOH N F NaCl F + NH3 + F HCl F F F N HO O
C C
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Mass Balance: Mass Balance of TFNA Kg Kg KOH 81 238 Effluent to ETP 2-Cyanoacetamide 332 ethyl 3-oxo 291 Formation of Step 1 trifluoroacetoacetate methanol 150 Water 399
Water 445 470 Effluent to ETP Formation of Step 2 POCl3 566
Sodium acetate 432 696 Effluent to MEE Formation of Step 3 69 Residue to Incinerator
Sodium Hydroxide 46 370 Effluent to ETP HCl 16 Formation of Step 4 87 LOD to incinerator Water 172 1000 TFNA
Total 2930 2930
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7. 5-Benzyl-1-Methyl, 2-Nitro 2 imino-tetrahydro 1, 3, 5-trizan Manufacturing Process: 1-Phenylmethanamine, Methylnitroguanidine & Formaldehyde are charged in the reaction mixture to form BNHT Chemical Reaction: NH2
O2N NH CH 3 HN N N H O + + O CH2 + 2 NH2 N N Methylnitroguanidine 1-phenylmethanamine Formaldehyde H BNHT NO2 Mass Balance:
Mass Balance of BNHT Kg Kg Water 873 1289 Effluent to ETP 1-Phenylmethanamine 446 Formation of 1000 BNHT Methylnitro Guanidine 446 BNHT Formaldehyde 524
Total 2289 2289
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8. 3-Aminomethyl tetrahydrofuran Manufacturing Process: 2-butene 1, 4-diol & 4-hydroxy 2-(hydroxyl methyl) butanal is added and agitated with H2SO4 and toluene, forming tetrahydrofuran -3-carbaldehyde mass. Ammonia is gradually added to agitator forming final product 3- Aminomethyl tetrahydrofuran. Chemical Reaction:
CHO CHO H SO 2 4 H O CO 2 HO + HO Toluene O H2 OH tetrahydrofuran-3-carbaldehyde OH 4-hydroxy-2-(hydroxymethyl)butanal 2-butene-1,4-diol
Raney Ni, Aq. NH 3
O
NH AETF 2
Mass Balance:
Mass Balance of AETF Kg Kg 2-butene-1,4-diol 855 Formation of Carbon monoxide 12 Step 1 Hydrogen 14
Sulfuric acid 15 144 Effluent to MEE Formation of Toluene 735 713 Toluene recovered Step 2 70 Residue to Incineration
Raney Nickel 1 674 Effluent to ETP Ammonia 292 Formation of 551 Ethyl Acetate Recovered Water 651 AETF 47 Residue to Incineration Ethyl Acetate 623 1000 AETF
Total 3198 3198
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9. 3-(dimethoxy phosphinothioyl sulfanyl methyl)-5-methoxy-1, 3, 4- thiadiazol-2-one Manufacturing Process: Step-1 Reaction of Phosphorous-pentasulfide with Methanol along with toluene and catalyst forms DMTP Step-2 Chloromethylation of M-Thiazone with paraformaldehyde and HCl gas along with EDC froms CMMT
Step-3 Reaction of CMMT and DMTP with conc. H2SO4 form final product MTN. Chemical Reaction
Step I
Toluene S OCH 3 P S 8 CH OH HS P 4 10 + 3 4 + 2 H2S TBAB catalyst Phosphorouspentasulphide OCH3 DMTP
Step II H Cl N N N N EDC O (CH O) HCl (gas) H O H3CO + 2 n + O + 2 S H3CO S
M-Thiazone Paraformaldehyde CMMT
Step III S OCH3 P S OCH3 Cl S Con. H SO N N N N OCH3 2 4 HCl + HS P O O + H3CO S H3CO S OCH3
MTN CMMT / EDC DMTP
M/s. PI Industries Ltd. 36
Mass balance:
Mass Balance of MTN Kg Kg Stage-I Toluene 436 34 Effluent To MEE P2S5 509 Formation of 425 Rec Toluene Methanol 293 DMTP 742 DMTP TBAB 5 42 NaSH by-product
Stage-II Dry HCl gas 171 33 Effluent to MEE EDC 1146 1723 CMMT solution in EDC Formation of CMMT M-Thiazone 353 Paraformaldehyde 86
CMMT solution in EDC 1723 592 Effluent to ETP (Stage-I) DMTP (Stage-I) 742 1236 EDC Distillate recycled Formation of 98% H2SO4 37 MTN 86 Residue to incineration
Water 287 1000 MTN EDC 125
Total 5913 5913
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10. (RS)-(O-2,4-dichlorophenyl O-ethyl S-propyl phosphorodithioate) Manufacturing Process:
Step-1 n-Propyl Mercaptane Phosphorus trichloride and sulful reacts together with MEP to forms Propyl phosphorodichlorido dithioate. Step-2 In second step K-500 and ethanol reacted with methlethyl pyridine along with toluene to form k-550. Step-3 K-550 treated with 2, 4-DCP and NaOH to form PTF.
Chemical reaction: Step I SH PCl S H C + 3 + 3 n-Propyl mercaptane Phosphorous trichloride Sulphur
MEP
S Cl P H3C Cl S + HCl Propyl phosphorodichloridodithioate
Step II
S CH S CH3 Cl 3 Toluene CH3 O H3C P + HO H C P CH S 3 3 + + S N Cl N Cl HCl CH CH3 3
K-500 Methylethyl pyridine K-550 Ethanol methylethyl pyridine.HCl
Step III
S H3C O HO S H3C P CH3 S S NaOH P Cl + + Cl Cl H3C O Cl H O NaCl O + 2 + MW 163 MW 345.24 Cl K-550 2,4-DCP PTF
M/s. PI Industries Ltd. 38
Mass Balance: Mass Balance of PTF Kg Kg Residue To Sulphur 76 36 Preperation of K- incineration PCl3 380 500 n-Propyl Mercaptane 150
Toluene 402 107 Effluent to ETP Preparation of K- Methyl Ethyl Pyridine 535 374 Toluene Recycled 550 Ethanol 108
2,4 Dichlorophenol 278 981 Effluent to MEE Preparation of NaOH 15 1000 Final PTF PTF DM water 555
Total 2498 2498
M/s. PI Industries Ltd. 39
11. Phosmet Manufacturing Process: Step-1 Phosfuruspenta sulfide and methanol forms Intermediate Step-2 Intermediate further treated with NaOH forms O, O-diethyl hydrogen dithiophosphate sodium salt. Step-3 1Hisoindole-1,3-(2H) dione and HCHO forms HMP. Step-4 HMP with Thionyl chloride forms mass of CMP Step-5 CMP treated with O, O-diethyl hydrogen dithiophosphate sodium salt form PNT along with NaCl. Chemical Reaction:
Step I OCH Catalyst HS 3 CH3OH + P2S5 P OCH + H2S S 3
O,O-dimethyl hydrogen dithiophosphate
Step II Na OCH3 OCH3 HS Na OH S P + P + H2O OCH OCH S 3 S 3
O,O-dimethyl hydrogen dithiophosphate sodium salt O,O-dimethyl hydrogen dithiophosphate
Step III O O
NH + CH 2O (Aq.) N OH
O O 1H-isoindole-1,3(2H) formaldehyde -dione 2-(hydroxymethyl)-1H-isoindole-1,3 (2H)-dione (Phthalimide (S)) (HMP)
Step IV O O
N SOCl 2 N SO2 HCl OH + + + Cl O Thionyl chloride O 2-(hydroxymethyl)-1H-isoin 2-(chloromethyl)-1H-is Sulfur dioxide dole-1,3(2H)-dione oindole-1,3(2H)-dione (HMP) (CMP) Step V
M/s. PI Industries Ltd. 40
O O S O Na P CH3 N S N + S + NaCl O CH3 Cl S P O O CH O O 3 H C Na-DMTA 3 2-(chloromethyl)-1H-is S-[(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)methy oindole-1,3(2H)-dione l] O,O-dimethyl dithiophosphate
(CMP) (PMT)
Mass Balance:
Mass Balance of PMT (Phosmet) Kg Kg Stage-I 23.5 % NaOH sol. 380 To caustic scrubber 492 27% NaSH-by product 328 H2S Gas
Methanol 295 10 Filter Solid to incinerator Phosphorous 536 36 Pre Cut recycle pentasulfide Formation of Na-DMTA Catalyst 2 88 Residue to incinerator Caustic 31 618 Na-DMTA
Stage-II Water 355 327 Effluent to ETP Phthalimide 370 Formation of HMP 708 HMP 37% formalin 310
Na-DMTA (Stage-I) 618 361 SO2+HCl Scrubber spent HMP (Stage-II) 708 Formation of CMPand 957 Effluent to ETP Thionyl Chloride 627 PMT, Crystallisation, 1000 PMT Water 308 Filtration and drying NaOH 56
Total 4596 4596
M/s. PI Industries Ltd. 41
12. 3-Methyl Antranilic Acid Manufacturing Process:
Step-1 2-Nitro 1, 3-diMethyl Benzene and Acetaldehyde react with each other in presence of oxygen and Acetic Acid forms 2-Nitro 3-Methyl Benzoic Acid. Step-2 2-Nitro 3-Methyl Benzoic Acid along with Hydrogen gas reacts with methanol. Agitation of the reaction mass provides the final product 3-Methyl antranilic acid. Chemical Reaction:
Step I
NO2 NO2 O O H C COOH 3 H O H3C CH3 + + 2 + + 2O H3C OH H3C H 2 Acetic acid
2-Nitro-3-methyl Acetic acid 2-Nitro-1,3-dimethyl benzene Acetaldehyde Oxygen benzoic acid
Step II
NO NH2 2 H C COOH H3C COOH 3 + 3H + 2H2O 2 Methanol 2-Nitro-3-methyl benzoic acid 3-Methyl anthranilic acid
Mass Balance:
Mass Balance of Q4039 Kg Kg Acetic Acid 1981 1942 Acetic acid recovered 2-Nitro-1,3- 757 910 Effluent to MEE dimethylbenzene Formation of Acetaldehyde 289 Step 1 DM Water 532 Oxygen 509
Methanol 1815 7 H2 to atmosphere Hydrogen Gas 25 Formation of 513 Effluent to ETP DM Water 234 Q4039 1770 Methanol recycled 1000 Q4039
Total 6142 6142
M/s. PI Industries Ltd. 42
13. 3-Methyl-2-Nitrobenzoic acid Manufacturing Process:
2-Nitro 1,3-dimethyl benzene along with acetaldehyde reacts with each other in addition to Co(CH3CO2)2 and Acetic Acid, in presence of air forms 3-Methyl-2- Nitrobenzoic acid. Chemical Reaction:
Air NO2 NO O 2 O Co(CH CO ) 3 2 2 H3C COOH H C CH 3 3 H C OH + 3 + H2O + H3C H + 2O2 Acetic acid 110°C 700-900 psgi YB449 Acetic acid 2-Nitro-1,3-dimethyl benzene Acetaldehyde MW 60.05 MW 151.16 MW 44.05 MW 181.14 MF C H O MF C H O MF C H NO 2 4 2 MF C8H9NO2 2 4 8 7 4
Mass Balance:
Mass Balance of YB449 Kg Kg Acetic Acid 357 547 Effluent to ETP 2-Nitro-1,3- Acetic Acid 840 Formation 343 dimethylbenzene recovered of Step 1 Acetaldehyde 264 156 LOD to incinerator DM Water 585 1000 YB449
Total 2046 2046
M/s. PI Industries Ltd. 43
14. 2-amino-5-chloro-N, 3-dimethylbenzamide Manufacturing Process: Step-1 2-Nitro 1, 3-diMethyl Benzene and Acetaldehyde react with each other in presence of oxygen and Acetic Acid forms 2-Nitro 3-Methyl Benzoic Acid. Step-2 Along with Hydrogen gas 2-Nitro 3-Methyl Benzoic Acid. Will reacts with Methanol and agitation provides final product 3-Methyl antranilic acid.
Step-3 Ethyl Chloro Formate along with toluene, NaOH and K2CO3 is agitated with 3-Methyl antranilic acid further to form Compound-C Na Salt. In this mass, hydrochloric acid is passed which removes the Sodium and forms Compound-C.
Step-4 Compound C is further treated with aq. HCl or H2O2 as oxidizing reagent and Acetic Acid forms compound-D. Step-5 Reaction of Compound-D with Methane sulphonic acid and Toluene reflux forms Compound E. Step-6 Compound E and Methylamine reacts together along with acetic acid or ethyl acetate to form intermediate which further converts to final product DPX. Chemical Reaction: Step I NO2 NO2 O O H C COOH 3 H O H3C CH3 + + 2 + + 2O H3C OH H3C H 2 Acetic acid
2-Nitro-3-methyl Acetaldehyde Oxygen Acetic acid 2-Nitro-1,3-dimethyl benzene benzoic acid
Step II NH2 NO2 H3C COOH H3C COOH 2H O + 3H2 + 2 Methanol
2-Nitro-3-methyl benzoic acid 3-Methyl anthranilic acid
M/s. PI Industries Ltd. 44
Step III
CH3 CH3 O NH2 NH2 Water Cl O CH + NaOH + 3 COOH COONa Ethylchloroformate DPX-Q4039 DPX-Q403Na-Salt MW 108.52 MW 151.16
Aq. NaOH Toluene Aq. K2CO3
CH3
NHCOOC 2H5 + NaCl COONa
Compound-C Na-Salt MW 58.5
HCl
CH3 NHCOOC 2H5 + NaCl COOH Compound-C MW 58.5 MW 223.22
Step IV
C H 3 CH3 NHCOOC 2H5 aq. HCl / H2O2 NHCOOC 2H5
+ 2 H2O COOH Acetic acid Cl COOH Compound-C Yield 90% Compound-D MW 223.22 MW 257.67
Step V CH 3 H CH3 N O NHCOOC 2H5 Methane sulphonic acid C H OH O + 2 5 Cl Cl COOH Toluene O Reflux Compound-D Compound-E MW 257.67 MW 211.60 MW 46
Step VI
CH O 3 H CH3 CH3 N O Ethylacetate / Acetic acid NH OH NH2
O H C NH CO2 + 3 2 NH NH + Cl Yield 95% Cl Cl CH3 CH3 O O 55-60oC O Compound-E Methylamine Intermediate DPX-G2S78 or Compound-F MW 211.60 MW 31.05 MW 198.64 MW 242.65
M/s. PI Industries Ltd. 45
Mass Balance:
Mass Balance of DPX Kg Kg Acetic Acid 762 383 Effluentto MEE Oxygen 36 729 Effluent to ETP 2-Nitro-1,3- 1004 Formation of 732 Acetic Acid recovery dimethylbenzene Step 1 Acetaldehyde 352 35 Residue to Incinerator DM Water 744 NaOH flaks 78
Methanol 1097 Formation of 1064 Methanol recycle H2 Gas 41 Step 2
Water 872 814 Toluene recovered Aq. NaOH 185 Aq. K2CO3 100 Formation of Toluene 857 Step 3 Ethyl chloroformate 80
HCL 55
Acetic Acid 969 372 Effluent to Incinerator Conc. HCl 16 416 Effluent to MEE Formation of Hydrogen Peroxide 57 616 Effluent to ETP Step 4 Na2SO3 8 930 Acetic acid recovery Water 213
Toluene 1771 1700 Toluene recovered Methane sulpfonic 20 Formation of 484 Effluent to ETP acid) Step 5 DM Water 228
Ethyl acetate 965 927 Ethyl acetate recycle Acetic acid 480 456 Acetic acid recovered Methylamine 228 Formation of setp- 250 LOD to incinerator DM Water 254 6 8 CO2 gas 555 Effluent to ETP 1000 DPX
Total 11471 11471
M/s. PI Industries Ltd. 46
15. 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid Manufacturing Process: Step-1 3-Chloro-2-hydrazinopyridine and diethyl maleate is mixed in agitator to form intermediateEthyl-(3-choropyridine-2-yl)-5ox-o-pyrazolidine-3-carboxylate Step-2 ACN and Potassium oxy bromine are added to this intermediate to form Ethyl-3-bromo-1-(3-chloropyridine–2-yl)-4, 5-oxo-pyrazolidine-3- carboxylate.
Step-3 Furthe H2SO4 is added with CH3CN to Ethyl-3-bromo-1-(3-chloropyridine – 2-yl) -4,5-oxo-pyrazolidine-3-carboxylate and agitated to form Ethyl-3-bromo- 1-(3-chloropyridine – 2-yl) 1-H pyrazole-5- carboxylate. Step-4 Ethyl group is substituted by Sodium Hydroxide to forms Sodium -3- bromo-1-(3-chloropyridine-2-yl) 1-H pyrazole-5- carboxylate. Hydrochoric acid is gradually added to the solution to remove the Sodium and to form final product 3-bromo-1-(3-chloropyridine-2-yl) 1-H pyrazole-5-carboxylic acid (BPCA). Chemical Reaction: Step I O
H2N NH CH O HN O 3 Cl N N O CH3 Cl O + + C2H5OH H3C O N O
3-Chloro-2-hydrazino Diethyl maleate Ethyl-(3-chloropyridin-2-yl)-5-ox pyridine o-pyrazolidine-3-carboxylate FW : 172:178 FW: 143.574 FW : 269.689
Step II O Br
N O CH3 HN O CH3 N N 3 ACN Cl O Cl O H PO N N + 3 4 3 + POBr3
Ethyl-(3-chloropyridin-2-yl)-5-ox Ethyl-3-bromo-1-(3-chloropyridin-2- o-pyrazolidine-3-carboxylate yl)-4,5-oxo-pyrazolidine-3-carboxya te FW : 269.689 FW : 332.581 Step III Br Br
N O CH3 N O CH3 N N O Cl O Cl H2SO4, Potassium Per Sulphate N N H CH3CN + 2
ethyl-3-bromo-1-(3-chloropyridin-2- ethyl-3-bromo-1-(3-chloropyridin-2- yl)-4,5-oxo-pyrazolidine-3-carboxyl yl)-1H-pyrazole-5-carboxylate ate FW : 330.565 FW : 332.581 Step IV
M/s. PI Industries Ltd. 47
Br Br
N O CH3 N ONa N N O Cl Cl O + C2H5OH N + NaOH N
ethyl-3-bromo-1-(3-chloropyridin-2- Sodium3-bromo-1-(3-chloropyridin-2-yl)- yl)-1H-pyrazole-5-carboxylate 1H-pyrazole-5-carboxylic acid
FW : 330.565 FW : 324.493
Br Br
N ONa N OH N N O Cl O HCl Cl NaCl N + N +
FW : 36.46 3-bromo-1-(3-chloropyridin-2-yl)-1H Sodium3-bromo-1-(3-chloropyridin-2-yl)- -pyrazole-5-carboxylic acid 1H-pyrazole-5-carboxylic acid FW : 302.512 FW : 58.44 FW : 324.493
Mass Balance:
Mass Balance of BPCA Kg Kg Water 752 3 chloro-2-pyridinone Formation of 460 732 Ethanol Recovered hydrazone Step 1 diethyl maleate 640
Acetonitrile 1770 Formation of 1717 Acetonitrile recovered phosphorous oxy bromide 760 Step 2 523 Effluent to ETP
Water 2105 250 Solid Waste to incinerator Acetonitrile 385 Formation of 122 Effluent to MEE Sulphuric Acid 760 Step 3 18 H2 to atmosphere potassium per sulphate 523 373 Acetonitrile recovery
Acetonitrile 868 850 Acetonitrile recovery Water 72 Formation of 2500 Effluent to MEE Sodium Hydroxide 160 Step 4 1525 Effluent to incineration HCl 355 1000 BPCA
Total 9610 9610
M/s. PI Industries Ltd. 48
16. 3-[2-[4-(1, 1-dimethylethyl) phenyl] ethoxy] Quinazoline Manufacturing Process:
Step-1 4-OHQ is added in solution of Thionyl Chloride in reactor to form 4-CQ Step-2 4-CQ and TBPE both chemical are treated in a reaction vessel to form FNZQ. Chemical Reaction:
Step-I
OH Cl
N N HCl + SOCl2 + SO2 + N N
4-OHQ Thionyl Chloride 4-CQ
Step-II OH CH3
H C CH O 3 3 Cl N N + + HCl CH3 N N H3C CH3 4-CQ TBPE FNZQ
Mass Balance: Mass Balance of FNZQ Kg Kg Caustic Solution 492 564 Scrubber spent to MEE 34 SO2 38 HCl Thionyl Chloride 1504 Formation of 4-OHQ 175 1420 Effluent to ETP Step 1 Water 954
TBPE 229 143 HCl By-Product Formation of Water 366 593 Effluent to MEE Step 1 1000 FNZQ
Total 3720 3720
M/s. PI Industries Ltd. 49
17. 2-ethyl-3, 7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolyl methyl carbonate Manufacturing Process: Step-1 PTC reacts with chorine and forms CMBC Step-2 CMBC reacts with IPA forms CMBP
Step-3 CMBP is treated with HNO3, MDC and Sulfuric Acid to form CMNBP
Step-4 CMNBP and TFMP are treated in an agitator with K2CO3 and DMAC to form NPBP. Step-5 NPBP autoclaved with hydrogen and methanol forms APBP Step-6 APBP treated with 3-Pentanol and Xylene forms PQO Step-7 PQO reacts with NaOH, TBAB, DMC and Toluene to forms FMTQ Chemical reaction: Step I O O Cl FeCl3 Cl Cl Cl2 HCl H3 C + H3 C + PTC CMBC Chlorine Hydrochloric acid Step II
O O CH3 CH3 Cl Cl Cl O CH3 HCl + HO CH3 + H C H3C 3 IPA CMBP CMBC Step III
O CH3 O CH3 Cl Cl O CH3 O CH3 H SO 2 4 + H2O + HNO 3 H3C NO2 H3C MDC
CMBP CMNBP
Step IV
O CH3 O CH3 OH Cl O DMAc O CH O CH3 K2CO3 3 + KHCO KCl F+CO + 3 + H3C NO2 3 F3CO H3C NO 2
CMNBP TFMP NPBP
M/s. PI Industries Ltd. 50
Step V
O CH3 O CH3 In Autoclave O O O CH3 O CH3
F3CO H3C NH2 2H2O F CO H C NO 3H2 + 3 3 2 + Methanol APBP NPBP Step VI
O CH3 O O O CH 3 Xylene H3C CH3 AlCl 3H O + + 3 + 2 F3CO H3C NH2
APBP 3-Pentanone
O
O CH3 CH3
HO H O 3HCl Al(OH)3 CH3 + + 2 + + F CO H C N 3 3 CH H 3 PQO Isopropanol
Step VII
O ONa O CH3 TBAB O CH3 + NaOH + H2O CH3 DMAC,Toluene F3CO H3C N CH3 H F3CO H3C N
PQO PQO-Na salt
O DMAC CH Toluene Cl O 3 MCF
O
CH3 O O O CH 3 + NaCl CH3 F3CO H3C N
FMTQ
M/s. PI Industries Ltd. 51
Mass Balance: Mass Balance of FMTQ Kg Kg PTC (p-Toluyl chloride) 462 Preparation of FeCl3 (Iron chloride) 2 86 HCl by-product CMBC Cl2 gas (Chlorine gas) 624
IPA 956 Preparation of 348 HCl by-product CMBP 494 Effluent to ETP
MDC 430 1198 Effluent to MEE H2SO4 183 Formation of 421 MDC-recycled HNO3 107 CMNBP 250 Residue to incinerator Water 193
DMAC 817 278 Effluent to ETP TFMP 581 800 DMAC-recycled Formation of NPBP K2CO3 45 Water 162
Methanol 191 262 Effluent to MEE Water 620 Formation of APBP 188 Methanol Recovered Hydrogen 3
Xylene 486 672 Effluent to MEE AlCl3 68 101 Residue to Incinerator 3-Pantanone 337 Formation of PQO 392 HCl by-product Sulfolane 314 471 Xylene recovered 337 Isopropanol recovered
DMAC 1485 395 Effluent to MEE Methyl chloroformate 243 1433 DMAC-recycled NaOH 20 241 LOD to incinerator Formation of FMTQ TBAB 40 225 Toluene recycled Toluene 237 1000 FMTQ Water 986
Total 9592 9592
M/s. PI Industries Ltd. 52
18. Dimethyl Cyanodithioimido Carbonate Manufacturing Process: Carbon Disulfide and Cyanimide are mixed with Methyl Chloride to form Dimethyl cyano dithioimido carbonate (CCITM) Chemical Reaction:
N S CH3 S S + N NH + 2 H C Cl 2HCl 2 3 N + S dimethyl CH3 Hydrochloric acid Carbon disulfide Cyanamide Methyl chloride cyanodithioimido carbonate
Mol. Formula = C S2 Mol. Formula = C H2 N2 Mol. Formula = C H3 Cl Mol. Formula = C4H6N2S2 Mol. Formula = HCl Mol. Wt = 76.143 Mol.Wt. = 42.040 Mol. Wt.= 50.487 Mol. Wt. = 146.23384 Mol. Wt. = 36.5
Mass Balance: Mass Balance of CCITM Kg Kg Aq. Cynamide 129 462 Effluent to Incinerator Carbondisulphide 448 Formation of 610 Effluent to ETP Methylchloride 810 CCITM 74 HCl by-product DM Water 759 1000 CCITM
Total 2146 2146
M/s. PI Industries Ltd. 53
19. 2-chloro-5-chloromethyl pyridine Manufacturing Process:
Step-1 3-Picoline when reacted with H2O2 and H2SO4 in a reaction vessel forms 3-Picoline –N-Oxide Solution. Step–2 This 3-Picoline-N-Oxide Solution is further treated with triethyl amine, benzoyl chloride and MDC to form CMP Isomers. Step–3 Chlorine gas along with CMP and AIBN gives 2-Chloro 5- Chloro Methyl Pyridine (CCMP) Chemical Reaction: Step I CH 3 CH3 H2SO4 H O + 2 2 + H2O N N Hydrogen O- 3 - Picoline Peroxide
3 - Picoline - N- Oxide
Step II
O Cl CH CH3 3 CH 3 CH3 + MDC + + N + + N H C CH Cl N N Cl - 3 3 O CMP 3- Picoline-N-Oxide CMP Isomer benzoyl chloride Triethyl amine
- CH3 O H + N O H C CH 3 3 Triethyl amine benzoate
- CH3 CH3 O H H O + NaCl + + NaOH HCl N + N O + H3C CH3 H3C CH3 O Sodium chloride
Sodium hydroxide Triethyl amine benzoic acid Triethyl amine benzoate
+ H2O
Water
M/s. PI Industries Ltd. 54
Step III CH3 Water Cl
Cl Cl + AIBN + H Cl Cl N Cl N
Chlorine gas 2-Chloro-5-methyl pyridine 2-Chloro-5-chloromethyl Hydrochloric (CMP) pyridine (CCMP) acid
Mass Balance: Mass Balance of CCMP Kg Kg Water 1028 997 Effluent to ETP Sodium Tungstate 10 97 Salts to incinerator Formation of Sulphuric Acid 93 Step 1 3-Picoline 927 Hydrogen Peroxide 812
MDC 739 724 MDC-recycled Triethyl Amine 989 959 Triethylamine recycled Formation of HCl 13 652 Benzoic acid recycled Step 2 Benzoyl Chloride 412 206 Effluent to MEE Sodium Hydroxide 31 423 Effluent to ETP
Water 50 345 Effluent to MEE Formation of Chlorine Gas 407 142 Residue to incinerator Step 3 AIBN 34 1000 CCMP
Total 5545 5545
M/s. PI Industries Ltd. 55
Herbicides and Intermediates 20. 2, 6-dimethylindanone Manufacturing Process: Step-1 Water along with Sodium Propionate, 4-Methyl Benzaldehyde and Propionic Anhydride is treated in a reactor. With further distillation followed by agitation gives an intermediate, C-acid. Step-2 C-acid is treated with Sodium Hydroxide; Nickel and Hydrogen gas along with water gives another intermediate DHC- Acid which is obtained after distillation and filtration of mass. Step-3 DHC- acid is now agitated with Phosphorous Trichloride and Toluene to form an intermediate DHC- Acid Chloride, which is obtained by distillation of the mass. Step-4 DHC-Acid Chloride is now treated further with water and Toluene to give the final product DMI followed by distillation and cooling. Chemical Reaction: Step I CHO COOH (CH CH CO) O + 3 2 2 +CH3CH2COONa CH CH COOH + 3 2 + CH3CH2COONa CH3 H3C H3C 4-Methyl bezaldehyde Propionic anhydride Sodium propionate C - Acid Mol. wt-120.4 Mol. wt-130.14 Mol. wt-96.07 Mol. wt-176.2
Step II COOH COOH Solvent: Toluene H CH + 2 CH3 3 H C H3C 3
(2E)-2-methyl-3-(4-Me-Phenyl) acrylic acid Hydrogen 2-Methyl-3-(4-Me-Phenyl) Propionic acid M.Wt-2.00 M.Wt-176.2 M.Wt-178.22 Step III COOH Solvent: Toluene COCl PCl CH + 3 3 CH H3C 3 + H3C
2-Me-3-(4-Me-Phenyl)propionic acid Phos.trichloride 2-Me-3-(4-Me-Phenyl)propanoyl chloride Mol-wt-178.22 Mol-wt-137.33 Mol-wt-196.67
H PO 3 3 + HCl Hydrochloric acid
Phosphorous acid Mol-wt-36.45 Mol-wt-82.0 0
Step IV
M/s. PI Industries Ltd. 56
O COCl Solvent: Toluene H3C CH HCl CH3 3 + H3C
2-Me-3-(4-methylphenyl) propanoyl chloride DMI Hydrochloric acid Mol.wt-196.67 Mol.wt-160.20 Mol.wt-36.46
Mass Balance: Mass Balance of DMI (2,6-dimethylindanone) Kg Kg Mixture of Sodium Propionic anhydride 1809 2934 Propionate & Propionic anhydride-sodium C-ACID Formation propionate recovery Sodium Propionate 1076 4-methyl benzaldehyde 1265 Water 466
Hydrogen 25 899 Effluent to ETP Caustic lye (30%) 346 DHC-Acid 1269 Toluene recycled DM Water 178 Formation Toluene 1295
PCl3 300 DHC-acid Chloride 1058 Rec.Toluene-recovery Toluene 1079 Formulation
Toluene 831 500 Effluent to MEE Water 188 806 Rec. Toluene recovery DMI Frationation 61 Residue to Incinerator 332 HCl by-product 1000 DMI
Total 8859 8859
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21. 2, 6-dimethyl-2, 3-dihydro-1H-inden-1-amine Manufacturing Process:
Step-1 DMI reacts with HCONH2 and HCOOH and produce the Intermediate. The Intermediate is further agitated with HCl and NaOH in a closed reactor which forms DMAI Isomers. Chemical Reaction: O O NH H3C H H3C HCOOH H2O CO2 CH3 + HCONH + + 2 + CH3
DMI Intermediate
O NH2 NH H3C H C H 3 NaCl HCOONa H O HCl CH3 + + + 2 CH3 + + 2NaOH
Intermediate DMAI
NH2 NH2 NH2 H C H3C H3C 3 CH3 CH3 + CH3
DMAI trans-DMAI cis-DMAI Mass Balance: Mass Balance of DMAI Kg Kg Organic layer to Formamide 852 312 Incinerator Formic Acid 333 762 Effluent to MEE Formation of DMI 454 672 Effluent to ETP Step 1 Water 920 1000 DMAI HCl 81 Caustic Soda 107
Total 2746 2746
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22. 3H-1, 2, 4-Triazol-3-one, 4-amino-2,4-dihydro-5-(1-methylethyl)- Manufacturing Process: Step-1 Isobutyric acid agitated with hydrazine hydrate and toluene form 2- methyl propane hydrazide. Step-2 2-methyl propanehydrazide reacts along with methylcarbonochloridate, NaOH and EDC forms methyl2-(2-methylpropanoyl) hydrazinacar boxylate. Step-3 The methyl2-(2-methylpropanoyl) hydrazine carboxylate is reacted with hydrazine forms IAT. Chemical Reaction:
O Step 2 Step 1 Cl O O OH NHNH2 methyl carbonochloridate NH N H .H O NH O + 2 4 2 + NaCl+H2O O NaOH+EDC O Hydrazine Toluene O methyl2-(2-methylpropanoyl)hydrazinecar hydrate 2-methylpropanehydrazide boxylate Isobutyric acid
N2H4.H2O Step 3
H N
N O CH3OH H O N + + 2
NH2 Mass balance: Mass Balance of IAT Kg Kg Toluene 1225 286 Effluent to MEE Formation of Iso Iso Butyric Acid 727 1201 Toluene-recycled Butyric Acid Hydrazine Hydrate 438 121 Residue to incinerator Hydrazide Titatnium Dioxide 26
1,2-dichloro Ethane 476 452 Effluent to MEE Formation of 1,2-dichloro ethane- Caustic Soda 67 781 hydrazine caboxilic recycle Methyl Chloroformate 452 acid 66 Residue to incinerator Water 778
Hydrazine Hydrate 235 Formation of 361 Effluent to ETP hydrazine caboxilic 157 Effluent to Incinerator acid 1000 IAT
Total 4425 4425
M/s. PI Industries Ltd. 59
23. Ethyl (2R)-2-{4-[6-chloro-1, 3-benzoxazol-2-yl) oxy] phenoxy} propanoate Manufacturing Process:
2,6-Dichloro-1,3-benzoxazole and ethyl propanoate derivative reacts with K2CO3 and toluene in an agitation reaction and forms FPES. Chemical Reaction:
O O O O CH3 N O K2CO3,Toluene N CH O CH3 3 Cl + O CH O 3 O Cl HO Cl 2,6-dichloro-1,3-benzoxazole ethyl (2R)-2-(4-hydroxyphenoxy) ethyl (2R)-2-{4-[(6-chloro-1,3-benzoxazol-2-yl) propanoate oxy]phenoxy}propanoate
2 KCl+ CO2 + H2O + Mass Balance: Mass Balance of FPES Kg Kg Toluene 2910 87 Residue Incinerator ethyl(2R)-2-(4-hydroxy 428 2823 Toluene recovered phenoxy)propanoate Polyethylene Glycol 32 Formation of 433 Effluent to ETP Potassium Carbonate 152 Step 1 1000 FPES Water 478 2,6-dichlorobenzene 344 oxazole
Total 4343 4343
M/s. PI Industries Ltd. 60
24. (2-{2-chloro-4-mesyl-3-[(RS)]-tetrahydro-2-furylmethoxymethyl} benzoyl)-cyclohexane-1, 3-Dione) Manufacturing Process: AE-513 is now treated with Xylene and Thionyl Chloride with Acetonitrile, Triethyl Amine and 1, 3-Cyclohexanedione. This mass is agitated after which addition of Acetone Cyanohydrins and Sodium Bicarbonate is done. Filtration and distillation process further give the final product AE-473.
Chemical Reaction:
Mass Balance:
Mass Balance of AE-473 ((2-{2-chloro-4-mesyl-3-[(RS)]-tetrahydro-2- furylmethoxymethyl} benzoyl)-cyclohexane-1, 3-Dione)) Kg Kg Emission 739 N2 + CO2
10% NaOCl Sol. 3997 Hypo 3772 Scrubber effluent to Scrubber MEE
NaOH 396 Caustic 684 Scrubber Effluent to Scrubber MEE 319 CO2 105 HCl 196 HCN 183 SO2 Xylene 1260 1239 Effluent to ETP AE-513 1022 43 Solid to Incineration Thionyl Chloride 400 1210 Recovered Xylene Acetonitrile 860 551 Residue to Incinerator 1,3 Cyclohexanedione 204 432 Recycled IPA Triethyl Amine 382 843 ACN recycled AE-473 Acetone cyanohydrin 28 1000 AE-473 Sodium Bicarbonate 15 Water 1330 HCl 88 Isopropanol 450 Caustic Flakes 81
Total 10513 10513
M/s. PI Industries Ltd. 61
25. 2-{2-chloro-4-(methylsulfonyl)-3-[(2, 2, 2-trifluoroethoxy) methyl] benzoyl} cyclohexane-1,3-dione Manufacturing Process: 747-Either treated with Thionyl Chloride along with toluene forms Acid Chloride derivatives which is further treated with 1, 3-CHD forms O-acyl intermediate. Acetone cyclohydrin is allowed in reaction vessel to form final product TMBT.
Chemical Reaction:
Cl Cl
HOOC Toluene ClOC CF O CF O 3 + 3 + SOCl2 HCl CH CH3 3 S S O O O O Acid chloride derivatie 747-Ether Thionyl chloride
O Toluene TEA O 1,3-CHD
O
O O Cl O Cl
O CF3 Acetone cynohydrin O O CF3 CH3 + CH (C H ) N.HCl O S 3 2 5 3 O S O O O TMBT O-Acyl intermediate
Mass Balance: Mass Balance of Tembutrion(TMBT) Kg Kg Toluene 1830 1794 Toluene-recycled Fromation of 747 Ether 566 Step-1 Thionyl chloride 200
Toluene 1764 683 Effluent to MEE Formation of 1,3 CHD 160 1711 Toluene-recovered Step-2 Triethyl amine 344
Cyanohydrine 118 Formation of 316 Effluent to ETP Water 520 TMBT 1000 TMBT
Total 5503 5503
M/s. PI Industries Ltd. 62
26. 2-chloro-4-(methylsulfonyl)-3-[(2, 2, 2-trifluoroethoxy) methyl] benzoic acid Manufacturing Process: AE-014 and TFE both raw materials treated with NaOH prills and ACN along with o-DCB to forms 747-Ether. Chemical Reaction:
Mass Balance: Mass Balance of 747-Ether Kg Kg ODCB 1378 865 Effluent to MEE AE-014 816 949 Effluent to ETP NaOH Prills 126 1344 Rec ODCB recovered Formation of 747 Acetonitrile 540 Ether 529 Rec ACN recovered Trifluoroethanol 713 1000 747-Ether Water 1089 HCl 25
Total 4687 4687
M/s. PI Industries Ltd. 63
27. 3-Chloro-2-Methylthioanisole Manufacturing Process: 35 % HCl solution is mixed with 3-Chloro-2-Methyl Aniline, NaNO2, Sodium Carbonate under controlled condition. The mass is then reacted with Sodium Methyl Mercaptane to carry out coupling reaction. Then EDC is charged to wash the reaction mass and separate the organic & aqueous layer. EDC is being recovered by distillation. The final product 2C6SMT is separated from the mass by fractionation under vacuum. Chemical Reaction:
CH 3 CH 3 Cl NH 2 Cl S Solvent: EDC CH 3 2H NaNO2 2 O + + 2 HCl +CH 3`SNa + 2 NaCl+ N2 + sodium methyl mercaptane 3-chloro-2-methylaniline Formula Weight = 141.59812 2C6 SMT Formula Weight = 172.67506 Mass Balance: Mass Balance of 2C6SMT(3-chloro-2-methylthioanisole) Kg Kg 3-chloro-2-methyl Residue to 410 140 aniline incinerator HCl 53 788 Effluent to MEE Sodium nitrite 480 761 Recovered EDC Formation of Sodium carbonate 7 1057 Effluent to ETP 2C6SMT EDC 777 1000 2C6SMT Sodium Methyl 1052 Mercaptane Water 967
Total 3746 3746
M/s. PI Industries Ltd. 64
28. 5-(methylamino)-2-phenyl-4-[3-(trifluoromethyl) phenyl] furan- 3(2H)-one Manufacturing Process: Step-1 (3-trifluoromethylphenyl) acetonitrile and ethyl phenyl acetate are treated with in an agitation reactor to form Phenyl butane nitrile compound. Step-2 Phenyl butane nitrile further treated with acetic acid forms APTPF Step-3 Reaction of APTPF with Methyl Amine forms final product Flurtamone Chemical Reaction: Step I O
N N O CH3 F F F + NaOEt F + C2H5OH +NaCl O F F
(3-trifluoromethylphenyl) Ethylphenylacetate 3-oxo-4-phenyl-2-[3-(trifluoromethyl)phenyl]butanenitrile acetonitrile
Step II
N NH2 F F F O F Br2, CH3COOH F H O F + 2 + 2HBr + CH3COOH O O 3-oxo-4-phenyl-2-[3-(trifluoromethyl)phenyl]butanenitrile 5-amino-2-phenyl-4-[3-(trifluoromethyl)phenyl]furan-3(2H)-one
Step III
H3C NH NH F F 2 F F O O F H C + 3 NH2 F NH + 3 O O
5-amino-2-phenyl-4-[3-(trifluorome Methyl amine Flurtamone thyl)phenyl]furan-3(2 H)-one
M/s. PI Industries Ltd. 65
Mass Balance: Mass Balance of FLURT Kg Kg 3-trifluoromethylphenyl 400 350 Effluent to ETP acetonitrile Formation of Sodium Ethoxide 400 Step 1 247 Effluent to MEE Ethyl Phenyl Acetate 310
Bromine 380 203 Efffluent to MEE Formation of Glacial Acetic Acid 665 600 Acetic Acid recovered Step 2 Water 138
Methylamine 413 223 Effluent to MEE NH3 solution as by- HCl 44 Formation of 607 product Step 3 Water 767 287 Effluent to ETP 1000 FLURT
Total 3517 3517
M/s. PI Industries Ltd. 66
29. Methyl (methylthio) Acetate Manufacturing Process: Methyl chloroacetate and Sodium Methyl Mercaptane reacts in a reactor and forms MTAA Chemical Reaction:
O O CH3 S H C S Cl CH3 3 NaCl + H3C Na + O O Methyl chloroacetate Sodium methyl mercaptane Methyl(methylthio)acetate M.W.=108.523 M.W. =70 M.W.=120.171
Mass Balance:
Mass Balance of MTAA Kg Kg DM Water 537 190 Effluent to MEE NaOH 65 97 Residue to incinerator Phosphoric Acid (H3PO4) 157 359 Effluent to ETP Tetrabutyl ammonium Formation of 24 681 Rec MDC bromide (TBAB) MTAA Methyl chloro acetate 604 1000 MTAA Sodium Methyl Mercaptane 246 MDC 694
Total 2327 2327
M/s. PI Industries Ltd. 67
30. 1-(3-chloro-4, 5, 6, 7- tetrahydropyrazolo [1, 5-a] pyridin-2-yl)-5- methyl (prop-2-ynyl) amino] pyrazole-4-carbonitrile Manufacturing Process: Step-1 TMOF and Malononitrile react with zinc chloride to form MMMN Step-2 1, 1, 7-TCHO and Hydrazine hydrate reacts and form Int-2a Step-3 Int-2A and MMMN and BMMM react together and form Int-3a Step-4 Int-3a and HCl oxidized with H2O2 forms Int 4a Step-5 Int-4a along with NaOH forms Int 4b Step-6 Int 4b treated with TMOF, TBAB and p-TSA forms Int-5c Step-7 Int 5c and proparygyl chloride treated with NaOH forms PYCL Chemical Reaction: Step I CN OMe CN ZnCl H OMe 2 + CN + 2MeOH H3C O OMe CN TMOF Malononitrile MMMN
CN CN CN n-butanol MeOH CN + CN n -Bu O + CN C H O H3C O 4 10 + H3C O Butanol MMMN BMMN MMMN
Step II Cl
+ 2 NH2 NH Cl 2 NH Cl Cl + 2HCl H O O HN + 2 N NH2 1,1,7-TCHO Hydrazine hydrate Int-2a
Step III
CN N NH Cl + N HN NH O MeOH + C4H10O N 2 CH Cl HN + NC 3 N CN H2N Int-2a MMMN+BMMN Int-3a Methanol Butanol
M/s. PI Industries Ltd. 68
Step IV Cl N N N HCl + H O N 2H O Cl + 2 2 + 2 HN Cl HN N N CN CN H N 2 H N Int-3a Int-4a 2
Step V Cl Cl N N N NaOH N Cl + + H2O + NaCl HN N N N CN CN H2N H N Int-4a Int-4b 2
Step VI Cl
N OMe N + OMe + TBAB + 2 H2O N OMe N CN TMOF H2N Int-4b
Cl
N N 2CH3OH TBAB HCOOH p-TSA H2O N + + + + + N CN Methanol HN CH Int-5c 3
Step VII
Cl Cl
N N N N HC Cl NaOH + NaCl N + + N +H2O N N CN sodium hydroxide CN HN N Int-5c Propargyl chloride H3C CH3 CH PYCL
M/s. PI Industries Ltd. 69
Mass Balance: Mass Balance of PYCL Kg Kg Malononitrile 577 830 Recovered Methanol Zinc chloride 1 115 Recovered n-Butanol Formation of Step 1 n-Butanol 561 Trimethylorthoformate 1113
Hydrazine Hydrate 531 643 n-butanol recycled 1,1,7-trichloroheptene-3- Nitrogen to Wet 458 597 one Scrubber Conc. HCl 50 Formation of Step 2 141 Effluent to ETP Water 152 51 Effluent to MEE Hydrogen Peroxide 188 149 HCl by-product NaOH Soln 55
Trimethylorthoformate 922 733 Effluent to ETP TBAB 27 Formation of Step 3 590 Recovered TMOF DM Water 262
Caustic Lye 167 646 Effluent to MEE Water 556 Formation of Step 4 338 Effluent to ETP Propargyl chloride 212 1000 PYCL
Total 5833 5833
M/s. PI Industries Ltd. 70
31. 3-[1-(3, 5-dichlorophenyl)-1-methylethyl]-3,4-dihydro-6-methyl-5- phenyl-2H-1,3-oxazin-4-one Manufacturing Process: Step-1 Mehtyl phenylacetate and Ethyl acetate reacts with Sodium Methanolate, Hydrochloric acid and Ethyl Acetate and forms EAPA. Step-2 EAPA reaction with Chloromethane and Magnesium Metal and TFH forms DCAL Step-3 DCAL treated with acetonitrile, sulfuric acid, sodium hydroxide forms DCAA Step-4 DCAA dissolved in hexanol with sodium hydroxide forms DCAM Step-5 DCAM treated with -1-methylethylamine and formaldehyde with solvent xylene forms DCIM. Step-6 EAPA and DCIM reaction in xylene forms MY-100 Chemical Reaction: Step I
H3C O O O Solvent: Ethyl acetate C2H5 2 CH3OH NaCl O CH3ONa HCl + CH3 + O + O + +
CH 3 H3C O
methyl phenylacetate ethyl acetate sodium methanolate EAPA M F = C H O M F = C H O M F = C H O 9 10 2 4 8 2 M F = CH3NaO 12 14 3 F W = 150.17 F W = 88.10 F W= 54.02 F W = 206.23
Step II
O CH3 H3C Cl Cl Cl 2 CH Cl 2+ + Solvent: THF HO HCl + 3 + Mg + 2H + MgCl2 +
Cl Cl 3,5-dichlorobenzoyl chloride chloromethane Magnesium Metal 2-(3,5-dichlorophenyl)propan-2-ol M F = C H Cl O 7 3 3 M F = CH3Cl M F = Mg F W = 209.45 F W = 50.48 F W= 24.3 M F = C9H10Cl2O F W = 205.08
M/s. PI Industries Ltd. 71
Step III
CH3 H C 3 CH Cl 3 H3C O Cl HO Solvent: Acetonitrile + CH3CN + H2SO4 + 2 NaOH NH 2 H O + Na2SO4 + 2 H3C Cl 2-(3,5-dichlorophenyl)propan-2-ol acetonitrile sulfuric acid sodium hydroxide Cl ( DCAA) sodium sulfate Water M F = C9H10Cl2O M F = C H N 2 3 M F = H2O4S M F = HNaO F W = 205.08 M F = C11H13Cl2NO M F = Na O S M F = H O F W= 41.05 F W = 98.07 F W = 39.99 2 4 2 F Wt= 246.13 F W= 142.04 F W= 18
Step IV
CH3 CH3 H3C H3C O Cl Cl
NH Solvent: Hexanol H N NaOH 2 + + CH3COONa H3C
Cl Cl ( DCAA) sodium hydroxide DCAM sodium acetate M F = C H NaO M F = C11H13Cl2NO M F = HNaO M F = C9H11Cl2N 2 3 2 F Wt= 246.13 F W = 39.99 F W = 204.09 F W = 82.03
Step V
CH CH3 3 H C N 3 H C Cl Cl 2 Solvent: Xylene H3C H N H O 2 + + H2O
Cl Cl ( DCIM) 1-(3,5-dichlorophenyl)-1-methylethylamine formaldehyde M F = C10H11Cl2N M F = CH O M F = C9H11Cl2N 2 F W = 216.10 F W = 204.09 F W = 30.025
Step VI
CH O 2 H3C O CH CH3 N 3 Cl N O CH + Xylene H3C OH 3 H C 3 Cl + H3C O H3C O Cl Cl EAPA DCIM MY-100 Ethanol
Molecular Formula = C H O 12 14 3 Molecular Formula = C H Cl N 10 11 2 Molecular Formula = C H Cl NO Molecular Formula = C H O Formula Weight = 206.26 20 19 2 2 2 6 Formula Weight = 216.1 Formula Weight = 376.27 Formula Weight = 46.06
M/s. PI Industries Ltd. 72
Mass Balance: Mass Balance of MY-100 (3-[1-(3,5-dichlorophenyl)-1-methylethyl]-3,4-dihydro-6-methyl- 5-phenyl-2H-1,3-oxazin-4-one) Kg Kg Stage-I Methyl phenyl Acetate 205 510 Ethyl Acetate recycled Ethyl acetate 536 129 Effluent to ETP Sodium Methanoate 359 Formation of EAPA 1030 EAPA Water 512 HCl 56
Stage-II 3,5-dichlorobenzoyl 217 205 Effluent to ETP Chloride Chloromethane 292 Fractionation of 1063 THF recycled Water 638 DCAL Magnesium metal 1 THF 1108
Acetonitrile 41 98 Effluent to MEE Sulphuric Acid 100 464 Incineration salt DM Water 401 Formation of DCAA Sodium Hydroxide 64
Hexanol 2126 504 Effluent to ETP Formation of DCAM NaOH 97 1956 Hexanol recycled
Formaldehyde 221 324 Effluent to MEE Xylene 506 Formation of DCIM 491 Xylene recovered 706 DCIM
EAPA (Stage-I) 1030 738 Effluent to ETP Formation of DCIM (Stage-II) 706 103 Xylene recovered MY_100 Xylene 106 1000 MY-1000
Total 9321 9321
M/s. PI Industries Ltd. 73
32. 3-[[(2, 5-dichloro-4-ethoxyphenyl) methyl] sulfonyl]-4, 5-dihydro- 5, 5-dimethylisoxazole Manufacturing Process: Step-1 2, 5 DCP reacts with Diethyl sulfate in presence of caustic lay in agitator reactor to form DCEB. Step-2 DCEB and Paraformaldehyde react in presence of acidic nature, so HCl is charged in reactor to maintain the acidity of mass and after reaction EBC is formed. Step-3 BIO and Thiourea reacts to each other in reactor to forms ITCA for next step. Step-4 ITCA reacts in presence of Caustic to convert into SIO. Step-5 EBC and SIO are charged in reactor, agitating the mass its forms ISB.
Step-6 ISB reacts with oxidizing agent H2O2. IPA is added to remove the impurity. After getting the lake palace the IPA was recovered through distillation process. Chemical Reaction: Step I
Cl Cl
Diethyl sulphate
HO Cl H5C2O Cl NaOH 2,5-DCP DCEB
Step II
(HCHO)n Cl Cl Cl 35 %aq.HCl
H5C2O Cl H5C2O Cl DCEB EBC
Step III
S O H N O N CH 2 N CH 3 3 HBr. H2N NH2 CH CH3 + HN 3 Br S
BIO Thiourea ITCA
M/s. PI Industries Ltd. 74
Step IV
O N CH O O 3 H N N CH NaBr H O 2 3 CH NH + + 2 HBr. 2 NaOH 3 + H2N 2 CH + NaS HN 3 S SIO
ITCA
Step V
N O CH3 Cl O Cl N CH Cl CH3 S 3 + CH3 NaCl NaS + H5C2O Cl H5C2O Cl EBC SIO ISB
Step VI O O CH CH N 3 N 3 O CH3 CH3 IPA Cl Cl 2H O S + 2H2O S + 2 2 H C O Cl O H5C 2O Cl 5 2 ISB Lake Palace
Mass Balance:
M/s. PI Industries Ltd. 75
Mass Balance of LP Kg Kg Stage-I DCP 161 200 Effluent to MEE NaOH 60 Formation of Step 25 Effluent to ETP Water 340 1 Diethyl Sulfate 183
Paraformaldehyde 176 Formation of Step 350 Effluent to ETP HCl 29 2 775 EBC Water 401
Stage-II Organic Layer to BIO 1292 752 Formation of Step Incinerator Thiourea 89 3 Water 420
NaOH 77 Formation of Step 209 Effluent to MEE 4 917 SIO
EBC (Stage-I) 775 323 Effluent to MEE Formation of Step SIO (Stage-II) 917 5 Water 589
Hydrogen Peroxide 455 884 Effluent to ETP IPA 890 543 LOD to incinerator Formation of LP 876 IPA Recovery 1000 LP
Total 6853 6854
M/s. PI Industries Ltd. 76
33. Pantoxazone Manufacturing Process: Step-1 A solution of para flurophenol in Ethylene DiChloride (EDC) is prepared in an agitated vessel. Now chlorine is fed to form reaction mass Step-2 Caustic lye along with Ethyl Chloro Formate treated with reaction mass as received from step-1. This mass is neutralized with caustic lye solution. Now to the reaction mass is added Ethyl Chloro Formate. When the feed is over mass is washed with water and is sent to next step. Step-3 In a vessel mixture of sulfuric acid and nitric acid is prepared and mass of Step-2 is received in a reactor; Nitrating mixture is now slowly fed into this mass forms an organic Mass Step-4 Reaction mass receive from step-3 is taken in a reactor. Hydrogen gas is fed in this mass. The reduced mass is sent for next step. Step-5 In a vessel Cyclo Pentyl Bromide is treated with caustic lye. Mass of Step-5 is added Cyclo Pentyl Bromide. Toluene is distilled off from the reaction mass. This mass is than sent to next step. Step-6 Toluene is taken and metal sodium is charged under nitrogen atmosphere and agitated. Ethyl alcohol is fed. Mass a mixture of ethyl chloro acetate & acetone is fed to get alkyl butanoate. The mass is than reacted with Alkyl Butanoate forms KPP. Chemical Reaction:
M/s. PI Industries Ltd. 77
M/s. PI Industries Ltd. 78
Mass Balance: Mass Balance of KPP (Pentaxozone) Kg Kg 4 Fluorophenol 620 1718 HCl byproduct Chlorine 430 1842 NaBr - byproduct Caustic 590 828 Effluent to ETP Solid waste to Ethyl Chloroformate 736 30 incinerator Sulphuric Acid 520 690 Toluene recycled Nitric Acid 582 KPP-314 1000 KPP-314 Hydrogen Gas 64 Chloroformate 670 Alkyl Bromide 536 Alkyl Butaneoat 200 Water 432 Toluene 728
Total 6108 6108
M/s. PI Industries Ltd. 79
34. Methyl Dichloro Phosphine Manufacturing Process: Step-1 Methyl Chloride, Aluminum Chloride and Phosphorus trichloride reacts with Diethyl phthalate forms mass of Methyldichlorophosphine. Step-2 Methyldichlorophosphine treated with n-Butanol forms final product MPBS Chemical Reaction: Step I O
PCl O CH3 CH3Cl + AlCl3 + 3 + O CH3 Methyl Chloride Aluminum chloride Phosphorous trichloride O Diethyl phthalate
Cl Cl AlCl Diethyl phthalate + H3C P 2 + 3 . Cl
Methyl dichlorophosphine Step II
O Cl O CH3 P HO CH + n-BuCl + HCl H3C P + 2 3 H C 3 H Cl Methyl dichlorophosphine n-Butanol Methyl phosphonic butyl ester
Mass Balance: Mass Balance of MPBS Kg Kg Phosphorous Phosphorous 2422 2373 trichloride trichloride-recycled AlCl3.Diethyl Phthalate- Aluminium Chloride 1176 Formation of 2469 recovery Step 1 Methyl Chloride 472 18 Residue to incinerator Diethyl phthlate 1558 13 Cut-1-recycled Yellow Phosphorous 176
N-Butanol 899 356 HCl By-product NaOH 657 Formation of 577 Effluent to ETP DM Water 333 Step 2 887 n-Butanol-recycled 1000 MPBS
Total 7693 7693
M/s. PI Industries Ltd. 80
35. N-(2 Chloro-4 Fluoro-5-((ethoxy carbonyl)-amino)-benzoyl)-N-iso- propyl-N-methyl-sulfamid Manufacturing Process: Step-1 Chlorine gas along with CFT, AIBN is agitated in a reactor to form an intermediate product CFN thereby producing 30% HCl as a byproduct. Step-2 CFN is then treated with DM water and Iron Chloride. The mass is then quenched with Chlorobenzene which is then treated with Sodium Hydroxide and water to form another intermediate product SLFD. Step-3 This intermediate SLFD is further treated with Hydrogen gas and water in presence of catalyst to form the final product PCM. Chemical Reaction: Step I
F F F
O2N Cl2 HNO3 / H2SO4
AZO INITIATOR Cl Cl Cl CH 3 CCl 3 CCl 3 2-chloro-4-fluorotoluene 2-chloro-4-fluorobenzotrichloride 2-chloro-4-fluoro-5-nitro benzotrichloride Step II
F Cl F Cl hydrolysis HCl H O + 2 + 2 Cl O N O2N CCl 3 2 O 1-chloro-5-fluoro-4-nitro-2-(trichloromethyl)benzene 2-chloro-4-fluoro-5-nitrobenzoyl chloride
Cl O H2N O NH gas S NH CH S 3 HCl 3 SO Cl HCl O O N CH + 2 2 N CH3 3 H3C + + CH H C H3C 3 3 CH CH3 3 N-isopropyl-N-methylamine N-isopropyl-N-methylsulfamide isopropyl(methyl)sulfamoyl chloride
F Cl H N O F Cl 2 S + HCl O + N CH3 NH O Cl H3C O2N S CH3 O N CH3 O2N O H C O 3 CH3 2-chloro-4-fluoro-N-{[isopropyl(meth 2-chloro-4-fluoro-5-nitr N-isopropyl-N-methylsulf obenzoyl chloride amide yl)amino]sulfonyl}-5-nitrobenzamide
M/s. PI Industries Ltd. 81
Step III
F Cl F Cl H C H C Step 4A 3 3 3H + 2 + 2H2O NH NH N CH3 Catalyst N CH3 NO2 S H2N S Methanol CH CH O O O 3 O O O 3
800-Cl-Sulfonamid Hydrogen 800-Cl-Anilin Water
F F Cl Cl Step 5A H C H3C Cl O CH3 O 3
NH H C NH CH N CH3 + 3 NH N 3 H2N S Toluene S O CH CH O O O 3 O O O 3 800-Chlorid 800-Cl-Anilin Ethyl Chloroformate + HCl Hydrochloric Acid Mass Balance:
Mass Balance of PCM (N-(2 Chloro-4 Fluoro-5-((ethoxy carbonyl)-amino)-benzoyl)-N- iso-propyl-N-methyl-sulfamid) Kg Kg Stage I 2,4-CFT 451 548 Effluent to ETP Chlorine gas 652 242 Effluent to MEE Formation of CFN Oleum 297 488 Recovered Ethanol Ethanol 508
Water 535 Formation of SLFD 175 Effluent to ETP intermediate-1 990 Intermediate-1
Stage II N-isopropyl-N- 495 196 Effluent to MEE methylamine Formation of SLFD NH3 112 186 HCl by-product intermediate-2 SO2Cl2 283 Water 282 790 Intermediate-2
Intermediate-1 990 642 Effluent to ETP (Stage-I) Intermediate-2 Formation of SLFD 790 165 Residue to Incinerator (Stage-II) Water 346
Methanol 320 Formation of 287 Methanol recovered Hydrogen 11 Intermediate-3
ECF 330 462 Effluent to ETP Toluene 163 158 Toluene recovered Formation of PCM 236 HCL by-product 1000 PCM
Total 6565 6565
M/s. PI Industries Ltd. 82
36. Ethyl 3-amino-4,4,4-trifluorobut-2-enoate
Manufacturing Process: Step-1 Ethyl trifloroacetate and ethyl acetate are charged in a reactor for agitation reaction with HCOONa to obtain ETFAA. Step-2 ETFAA treated with ammonium acetate along with acetic acid produce EATB. Chemical reaction:
Step I
O O O O + + CH3CH2OH F3C O O HCOONa F3C O
ethyl trifluoroacetate ethyl acetate ETFAA
Step II
O O NH2 O CH COONH H O F3C O + 3 4 + CH3COOH + 2 AcOH F3C O ETFAA EATB
Mass Balance: Mass Balance of EATB Kg Kg ETFA 558 1353 Distillate recycled Ethyl Acetate 493 248 Residue to incinerator Sodium Ethoxide 283 323 Effluent to ETP Formation of Acetic Acid 354 1000 EATB Step 1 Ammonium Acetate 570 Sodium Bicarbonate 98 Water 568
Total 2924 2924
M/s. PI Industries Ltd. 83
37. 2, 6-bis (4,6-dimethoxypyrimidin-2-yloxy)benzoic acid Manufacturing Process: DHBA and DMMSP are agitated with NaH and THF to form BPS. Chemical Reaction: COONa O OH H CO H3CO N O O N OCH3 3 OCH3 HO OH N N THF N N + 2 CH3SO2Na + 3 H2 + 2 + 3 NaH O S O OCH OCH3 3 CH3 BPS Na-Salt MSA DHBA DMMSP Sodium hydride MW 452.35 MW 102.08 MW 154.12 MW 218.23 MW 24
Mass Balance:
Mass Balance of BPS Kg Kg THF 617 18 H2 to atmosphere NaH 200 669 Effluent to ETP Formation of DHBA 253 598 THF recovery Step 1 DMMSP 770 1000 BPS Water 445
Total 2285 2285
M/s. PI Industries Ltd. 84
38. N, N-Dimethyl-2-[N-[N-(4, 6-dimethoxypyrimidin-2-yl)- aminocarbonyl] aminosulfonyl]-4-(N-formylamino) benzamide, sodium salt Manufacturing Process: Step-1 PCF and ADMP react with each other with mixture of TFH and forms ADMP Carbamate Step-2 The reaction with NSA and ACN of ADMP carbamate produce NSU
Step-3 Reaction of NSU along with Hydrogen, NaMoO4 and H2SO4 produce ASU. Step-4 ASU, Formic Acid and acetic anhydride reacts in a reaction vessel. On further addition of Acetone FRSF is obtained. Step-5 FRSF is reacted with sodium methoxide and acetone forming final product FRSF-Na. Chemical Reaction:
Step-I
CH3 CH3 O O
O N O N THF + HCl + CH3 CH3 O NH N O O Cl H2N N O
ADMP Carbamate Hydrochloric acid PCF ADMP
Step-II
H3C CH3 N CH3 H3C CH3 O N OH O ACN O N O + NH K2CO3 N 2 NH N O KHCO O + O N S + + 3 NH 2 CH O N O N S 3 O O O CH N 3 O O OK
O NSU CH3 Phenol ADMP Carbamate NSA
Step III
H3C CH3 N H3C CH3 N
O O
N NH N O O N S 2 CH 3 H NH NH N O 2 H O KHSO +3 2 NaMoO H SO S + 2 + 4 4 2 4 H2N O O CH3 N OK O O N O O
CH3 O ASU CH3 NSU
M/s. PI Industries Ltd. 85
Step IV
H C CH H3C CH3 3 3 N N
O O
HCOOH Ac O NH NH NH N O 2 Acetone NH N O S + + NH S + 2CH3COOH H N CH CH 2 3 O 3 O O O O N Acetic anhydride N O O
O Formic Acid O CH CH3 3 ASU FRSF
Step V
H3C CH3 H3C CH3 N N
O O Na NaOMe - N NH N O + Acetone NH S + CH3OH NH NH N O CH NH S 3 CH O O O 3 O O O N N O O O
O CH3 CH3 FRSF Sodium Methoxide FRSF-Na
M/s. PI Industries Ltd. 86
Mass Balance:
Mass Balance of FRSF-FSS Kg Kg Water 522 539 HCl by-product Scrubber 17 HCl THF 832 199 Effluent to ETP Formation of ADMP 272 33 LOD to Incinerator Step 1 Phenyl chloroformate 423 799 THF Recyled
Acetonitrile 2200 2145 Acetonitrile-recycled NSA 490 Formation of K2CO3 92 Step 2 Water 1050
Water 406 806 Effluent to MEE Formation of Hydrogen Gas 22 1100 Effluent to ETP Step 3 Sulphuric Acid 69 435 Effluent to Incinerator
Formic Acid 335 Formation of Acetic anhydride 368 272 Acetone-Recovery Step 4 Acetone 278
Acetone 330 216 Effluent to MEE Sodium Methanoate 280 Formation of 102 LOD to incinerator Step 5 323 Acetone-Recovery 1000 FRSF/FSS
Total 7970 7970
M/s. PI Industries Ltd. 87
39. 3-ethylsulfonyl-2-pyridine sulfonamide Manufacturing Process: Step-1 3-AMP reacts with aq. HCl and NaOH along with Chlorine Gas and forms CAMP.
Step-2 CAMP further treated with NaNO2 and NaHSO3 forms CAPS
Step-3 CAPS with K2CO3, NaHCO3, NaSO3 and C2H5Br is charged in agitation reactor to form CESP. Step-4 CESP further reacted with NaSH, chlorine Gas and Ammonia Gas in presence of hydrogen forms finals product 3-ethylsulfonyl-2-pyridine sulfonamide. Chemical Reaction: Step I
NH2 Aq.HCl NH2 Cl + 2 +NaOH NaCl H O N + + 2 N Cl
3-AMP CAMP Step II O NH Cl 2 S 3 H Cl NaHSO , + + NaNO2 + 3 O N2 2 NaCl N Cl + + +3H2O N Cl CAMP CAPS
Step III O Cl S O O K CO S Na SO 2 3 + 2 3 + NaHCO3 C H Br O N Cl + 2 5 CO NaBr NaCl SO H OH + 2 + + + 2 + N Cl CAPS CESP
Step IV
O O S S O NaSH, 2Cl2 6 NH3 + H O O + + + 2 + 2 O NaOCl 4NH Cl N Cl + + 4 N S NH2 CESP O O ESPS
M/s. PI Industries Ltd. 88
Mass balance: Mass Balance of ESPS Kg Kg 3-Aminopyridine 378 20 Effluent to ETP DM Water 384 HCl 44 Formation of Step 1 Ferric Chloride 1 Chlorine gas 84 Sodium Hydroxide 75
Sodium Bisulfite 281 510 Effluent to MEE Sodium Nitrite 213 HCl 42 Formation of Step 2 DM water 201 Copper chloride 1
Caustic solution 158 185 Spent to MEE
27 SO2 Sodium Sulfite 337 609 Effluent to MEE Sodium bicarbonate 18 Water 82 Formation of Step 3 Ethyl Bromide 37 Potassium carbonate 23
NaSH 202 530 Effluent to ETP Chlorine Gas 219 611 Effluent to Incinerator Formation of ESPS Water 582 1000 ESPS Ammonia 103
Total 3465 3465
M/s. PI Industries Ltd. 89
40. Methyl 2-amino-4-{[(methylsulfonyl) amino] methyl}benzoate Manufacturing Process: Step-1 Reaction is carried out between Methyl 4-cyano 2-nitrobenzoate and HCl charging hydrogen gas, Toluene and CAcOH to produce Intermediate. Step-2 Methane sulfonyl chloride and trimethyl amine along with thionyl chloride is added to intermediate and agitated further to produce final Product. Chemical Reaction:
Step I
O O O O
NH2 NO2 i) CAcOH + 5 H + HCl + 2 H2 ii) Toluene
CN HCl NH2
methyl 4-cyano-2-nitrobenzoate
Step II O O O O NH MeSO2Cl 2 O NH2 Et3N + S Cl + 2 Et3 + 2 Et3 O DMAc NH HCl NH2 O S O
AMSB
Mass Balance: Mass Balance of Mesylamid Kg Kg Methyl 2-nitro 4- 627 712 Toluene recycled cyanobenzoate Acetic acid Acetic Acid 969 895 Formation Step 1 recycled Hydrogen Gas 23 Toluene 727 HCl Gas 66
DMAC 800 768 DMAC recycled Triethyl Amine 560 1372 MDC recycled methanesulfonyl 320 688 Effluent to MEE chloride Formation Step 2 Water 1067 1124 Effluent to ETP MDC 1400 1000 Mesylamid
Total 6559 6559
M/s. PI Industries Ltd. 90
41. 2-(trifluoromethoxy) aniline Manufacturing Process: Step-1 Bromine along with trifluromethoxy benzene forms 4-bromophenyl trifluoromethyl ether
Step-2 4-bromophenyl trifluoromethyl ether treated with H2SO4, MDC with fuming HNO3 forms mass of 4-bromo 2-nitrophenyl trifloromethyl ether and 4- bromo 3-nitrophenyl trifloromethyl ether Step-3 Mass of 4-bromo 2-nitrophenyl trifloromethyl ether and 4-bromo 3- nitrophenyl trifloromethyl ether along with hydrogen gas forms the final product Chemical Reaction: Step I F F O F O F Br + 2 F + HBr F Br
Trifluoromethoxy benzene Bromine 4-bromophenyl trifluoromethyl ether
Step II
- O + O - N O F F + F O F O F N O F H2SO4 O + Fuming HNO3 + F MDC F F Br Br Br
4-bromophenyl trifluoromethyl ether 4-bromo-2-nitrophenyl 4-bromo-3-nitrophenyl - 2H2O trifluoromethyl ether trifluoromethyl ether
Step III
- O + O - N O NH2 F F F + F H N O F O F N O F O F 2 O 2 H2O HBr + + F + + F F 4 H F Br Br 2 4-bromo-2-nitrophenyl 4-bromo-3-nitrophenyl 2-(trifluoromethoxy)aniline 3-(trifluoromethoxy)aniline trifluoromethyl ether trifluoromethyl ether
M/s. PI Industries Ltd. 91
Mass Balance: Mass Balance of OTMA Kg Kg Trifluoromethoxy 1219 761 HBr By-Product benzene Formation of step-1 Bromine 1203
Fuming Nitric Acid 205 339 Effluent to ETP Sulphuric Acid 22 Methylene Formation of step-2 185 Dichloride DM Water 521
Hydrogen Gas 75 761 HBr By-product 339 Efluent to MEE Formation of OTMA Residue to 232 Incinerator 1000 OTMA
Total 3431 3431
M/s. PI Industries Ltd. 92
42. Cyanazine Manufacturing Process: Step-1 2-hydroxy 2-mrthyl propanenitrile and ammonia gas react with each other in a reactor from 2-amino 2-methylpropanenitrile. Step-2 2, 4, 6-trichloro-1, 3, 5-triazine react with 2-amino 2- methylpropanenitrile and forms CNZ. Step–3 CNZ wash with DM water and form final product CNZ.
Chemical Reaction:
Step I
N N HO H2N
NH3 + H2O H3C H3C CH3 CH3
2-hydroxy-2-methylpropanenitrile 2-amino-2-methylpropanenitrile
AMP
Step II
CH3 N Cl N Cl NH N
N H3C CH3 HCl N N + + Cl N NH2 H C N Cl 3 Cl 2,4,6-trichloro-1,3,5-triazine 2-amino-2-methylpropanenitrile CNZ-I
Step III
CH3
CH3 NH N
NH N N CH3 N Cl N CH3 + HCl Aq. Ethyl amine solution Cl N + N H2O N NH
Cl CH3
CNZ-II
M/s. PI Industries Ltd. 93
Mass Balance: Mass Balance of CNZ(Cynazine) Kg Kg 2-hydroxy-2- 693 Formation of 845 Effluent to MEE methylpropanenitrile intermediate-1 Ammonia 481
2,4,6-trichloro-1,3,5- 939 300 Effluent to ETP triazine Formation of CNZ-I 145 HCl By-product
DM Water 787 422 Effluentto ETP Aq. Ethyl amine 281 Formation of CNZ 468 HCl by-product 1000 CNZ
Total 3180 3180
M/s. PI Industries Ltd. 94
43. N-(5, 8-dimethoxy [1, 2, 4] triazolo [1, 5-c] pyrimidine-2-yl)-2- fluoro-6-(trifluoromethyl) benzenesulfonamide Manufacturing Process: Step-1 1, 4 dimethoxy benzene and Ethyl carbon isothiocyanatidate and carbonate compound in reactor to form Intermediate. Step-2 The intermediate is treated with FTBSC to form final Product DTPBS
Chemical reaction: Step I
N O CH S 3 CH CH 3 3 CH3 O O O O ethyl carbonisothiocyanatidate NH NH O CH NH 3 2 NH NH O CH3 N N N O N N N N S O HO ethyl [(2,5-dimethoxypyrimidin-4-yl) carbamothioyl]carbamate O O O H C H C 3 3 H3C 1,4-dimethoxybenzene SH + H
CH3 Step 2 O
N H O CH3 NH2 H OH N N + + N O O ethyl formate H3C 5,8-dimethoxy[1,2,4]triazolo [1,5-c]pyrimidin-2-amine Step II
CH3 CH3 O O N NH O N F S NH N 2 N N HCl N N O N O CF3 + Cl S O F C O 3 H3C H3C O 5,8-dimethoxy[1,2,4]triazolo N-(5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-yl)- [1,5-c]pyrimidin-2-amine F 2-fluoro-6-(trifluoromethyl)benzenesulfonamide FTBSC
M/s. PI Industries Ltd. 95
Mass Balance:
Mass Balance of DTPBS Kg Kg Water 360 406 HCl by-product
46 HCl 4-amino-2,5- 600 1337 Effluent to ETP dimethoxypyrimidine ethoxy carbonyl 583 110 LOD to incinerator isothiocyanate Formation of Step 1 Toluene 38 deionized water 57 hydroxylamine 154 Water 196 Methanol 258
Toluene 223 219 Effluent to ETP 2-fluoro-6- (trifluoromethyl) 588 268 Effluent to MEE benzenesulfonyl Formation of Step 2 chloride Water 498 215 Toluene recycled 1000 DTPBS
Total 3555 3555
M/s. PI Industries Ltd. 96
Fungicides and intermediates 44. (2E)-2-(Methoxyimino)-N-Methyl-2-(2-Phenoxyphenyl) Acetamide Manufacturing Process: Step-1 Phenol reacts with 1, 2-dichlorobenzene and potassium hydroxide and forms 1-chloro-2-phenoxybenzene. Step-2 1-chloro-2-phenoxybenzene further treated with magnesium, THF or Xylene in presence of Ethyl bromide forms Grignard mass which with further addition of water forms butyl oxo (2-phenoxyphenyl) acetate. Step-3 Methyl amine is further added to butyl oxo (2-phenoxyphenyl) acetate forms N-methyl-2-oxo-2-(2-phenoxyphenyl) acetamide. Step-4 N-methyl-2-oxo-2-(2-phenoxyphenyl) acetamide treated with hydroxylamine sulphate forms (2E)-2-(Hydroxykmino)-N-methyl-2-(2- phenoxyphenyl) acetamide. Step-5 (2E)-2-(Hydroxykmino)-N-methyl-2-(2-phenoxyphenyl) acetamide treated with dimethyl sulphate and potassium carbonate forms the final product. Chemical Reaction: Step I
OH Cl Cl
Cl O
+ + KOH + KCl + H2O
Phenol 1,2-dichlorobenzene 1-chloro-2-phenoxybenzene Step II
Cl COCOOBu MgCl O O THF / Xylene O + Mg + BuOH + Mg(OH)Cl Ethyl Bromide H20 butyl oxo(2-phenoxyphenyl)a 1-chloro-2-phenoxybenzene Grignard mass cetate MW : 76.8
Step III
COCOOBu COCONHCH 3
O O 40 % MeNH2 + BuOH
butyl oxo(2-phenoxyphenyl)acetate N-methyl-2-oxo-2-(2-phenoxyphenyl)acetamide
M/s. PI Industries Ltd. 97
Step IV
HO O O O N (NH2OH)2.H2SO4 NH NH + H2SO4 H2O NH2OH + HCL CH3 + CH3 30% HCL O O N-methyl-2-oxo-2-(2-phenoxyphenyl) (2E)-2-(hydroxyimino)-N-methyl-2- acetamide (2-phenoxyphenyl)acetamide
Step V
CH3 HO O N O (CH3)2SO4 O N NH CH NH 3 H O/K CO 2 2 3 CH3 O O
(2E)-2-(hydroxyimino)-N-methyl-2- (2E)-2-(methoxyimino)-N-methyl-2- (2-phenoxyphenyl)acetamide (2-phenoxyphenyl)acetamide Mass Balance: Mass Balance of SSF-126-OXIME Kg Kg 1,2-dichloro benzene- Molten Phenol 442 1385 recovery 1,2-dichloro benzene 1406 Formation of Step 1 KOH 117 Water 52
Xylene 1447 Magnesium Turnings 8 1404 Xylene-Recovery Ethyl Bromide 20 Formation of Step 2 Di Butyl Oxalate 476 Water 378
Methylamine 582 1120 Effluent to MEE Formation of Step 3 Water 521
Hydroxyl amine 255 765 Effluent to ETP sulphate Formation of Step 4 HCl 79 84 LOD to incinerator
Potassium Carbonate 13 850 Effluent to ETP Dimethyl Sulphate 233 Formation of Step 5 56 LOD to Incinerator Water 636 1000 SSF-126/OXIME
Total 6664 6664
M/s. PI Industries Ltd. 98
45. N, N'-[1, 4-Piperazinediyl-Bis (2,2,2-Trichloroethylidene)]-Bis- [Formamide] Manufacturing Process: Step-1 Trichloroacetaldehyde and Formamide together forms 2,2,2-trichloro-1- hydroxy ethylformamide Step-2 2, 2, 2-trichloro-1-hydroxy ethylformamide treated with Phosphorus Trichloride forms 1,2,2,2-tetrachloro ethylformamide. Step-3 1, 2, 2, 2-tetrachloro ethylformamide treated with Piperazine forms TRFRN
Chemical Reaction:
M/s. PI Industries Ltd. 99
Mass Balance: Mass Balance of TRFRN (Triforine) Kg Kg Trichloroacetaldehyde 849 Formation of step-1 Formamide 251
Phosphorous 538 278 Effluent to MEE Trichloride Formation of step-2
Piperazine 656 1242 n-Butyl acetate Byproduct TRFRN formation Water 622 397 Effluent to ETP 1000 TRFRN
Total 2917 2917
M/s. PI Industries Ltd. 100
46. N-(1-Cyano-1, 2-Dimethylpropyl)-2-(2,4—Dichlorophenoxy) Propanamide Manufacturing Process:
Step-1 DCPPA reacts with SOCl2 forms DCPPA-Cl Step-2 DCPPA-Cl and ADMBN when treated with each other form FNXL in
combination with NaCl, CO2 and H2O. Chemical Reaction: Step-I
O O O O OH Cl SOCl2 CH3 + CH3 SO HCl Cl Cl Cl Cl + 2 +
DCPPA DCPPA-Cl
Step-II
O CH3 NaHCO O NC O H C CN 3 Cl 3 O CH NH 3 NH2 CH3 CH3 NaCl CO H O Cl Cl + CH3 + + 2 + 2 H C Cl Cl 3 CH3 DCPPA-Cl ADMBN FNXL
Mass Balance: Mass Balance of FNXL Kg Kg Scrubber effluent to Caustic solution 264 321 Caustic scrubber MEE
21 HCl 37 SO2 DCPPA 800 302 Residue to solid incinerator Formation of DCPPA-Cl Toluene 900 882 Toluene Recovery Thionyl Chloride 430
ADMBN 445 217 Residue NaHCO3 2 577 Effluent to ETP Formation of FNXL Water 450 1000 FNXL NaOH 8
Total 3299 3299
M/s. PI Industries Ltd. 101
47. (1E)-1-(2, 5, 5-Trimethyl-1,3-Dioxan-2-yl)Propane -1,2-Dione 1- (O-Methyloxime) Manufacturing Process: Step-1 Sulphuric Acid & Sodium Nitrite are charged in the reaction mixture of Acetyl acetone & DM water & further MTBE (Methyl tert-Butyl Ether) is charged in the above mixture to form HIPD, an intermediate. Step-2 HIPD is charged in mixture of MTBE, Potassium Carbonate, DMF, and Dimethyl Sulphate and then methylation is being done in presence of DMA to form intermediate. Step-3 The intermediate from step-2 is being added into mixture of toluene, Neopentyl Glycol & TSA under agitation to form final product MIPD. Chemical Reaction:
Step-I O O O O Na SO 2 H O 2 2 2 + 2 4 + 2 + NaNO 2 + H2SO 4 H C CH3 H3C 3 mw:142.03 CH3 mw:68.99 mw:98.07 Acetyl N acetone OH HIPD mw:100.116 pentane-2,3,4-trione 3-oxime mw:129.114 Step-II
O O O O
K CO (CH3)SO4 CH 2 3 + H3C 3 + CH H3C 3 mw:126.127 N mw:138.18 OH N OCH 3 MIPD HIPD pentane-2,3,4-trione 3-(O-methyloxime) pentane-2,3,4-trione 3-oxime mw:143.141 mw:129.114
CH KSO + KHCO 3 + 3 4 potassium potassium bicarbonate methyl sulfate mw:100.12 mw:150.20 Step-III
O O CH H3C O 3 CH3 H3C N H C CH HO CH CH OH 3 3 2 2 O + H2O O CH3 N CH3 OCH 3 H C Neopentyl glycol 3 O mw:104.148 MIPD (1E)-1-(2,5,5-trimethyl-1,3-dioxan-2-yl) M/s. PI Industries Ltd. propane-1,2-dione 1-(O-methyloxime) 102 pentane-2,3,4-trione 3-(O-methyloxime) mw:229.273 mw:143.141 MIPD-ketal Step-I O O O O Na SO 2 H O 2 2 2 + 2 4 + 2 + NaNO 2 + H2SO 4 H C CH3 H3C 3 mw:142.03 CH3 mw:68.99 mw:98.07 Acetyl N acetone OH HIPD mw:100.116 pentane-2,3,4-trione 3-oxime mw:129.114 Step-II
O O O O
K CO (CH3)SO4 CH 2 3 + H3C 3 + CH H3C 3 mw:126.127 N mw:138.18 N OH OCH 3 MIPD HIPD pentane-2,3,4-trione 3-(O-methyloxime) pentane-2,3,4-trione 3-oxime mw:143.141 mw:129.114
CH KSO + KHCO 3 + 3 4 potassium potassium bicarbonate methyl sulfate mw:100.12 mw:150.20 Step-III
O O CH H3C O 3 CH3 H3C N H C CH3 HO CH 2 CH 2 OH O H O 3 CH + 2 O 3 N CH3 OCH 3 H C Neopentyl glycol 3 O mw:104.148 MIPD (1E)-1-(2,5,5-trimethyl-1,3-dioxan-2-yl) propane-1,2-dione 1-(O-methyloxime) pentane-2,3,4-trione 3-(O-methyloxime) mw:229.273 mw:143.141 MIPD-ketal
Mass Balance: Manufacturing process of MIPD Kg Kg DM Water 482 338 Effluent to ETP Acetyl Acetone 543 Sulphuric Acid 106 NITROZATION Sodium Nitrite 563 NaCl 32
Potassium Carbonate 2 1260 Effluent to MEE Dimethyl Sulphate 445 METHYLATION Dm Water 358
NPG 90% 801 152 Effluent to ETP MIPD-KETAL Recovered NPG to Dm Water 188 770 FORMATION Incinerator 1000 MIPD-Ketal
Total 3520 3520
M/s. PI Industries Ltd. 103
48. Orysastrobin Manufacturing Process: Step-1 Oximether reaction is carried out between Aqueous Methoxy Amine Hydrochloride and MIPD Ketal at room temperature and atmospheric pressure. Toluene is used as a solvent which is distilled off to get the Step1 product in crude form. Step-2 Hydroxyl Ammonium Sulphate is reacted with above product in presence of catalyst and Sulphuric Acid is used to maintain the pH of the reaction mass. Isopropyl Alcohol and Toluene are used as solvent which are distilled off giving step II product in crude form. Step-3 Methylamide is formed by addition of Sodium Methylate to above intermediate. Distillation of mass helps recovering Methanol and giving final product ORST. Chemical reaction: Step I
CH3 CH3 HO O O O N N Cl N N O O 2CH OH NaCl CH ONa O O CH NH H3C CH3 N CH 3 + H3 C CH3 3 + 3 2 3 + + + N CH3 N N N O O H O H3C H3C CH3 CH3 BOO-EZE/EZZ/EEE CLMO ORST-EEEE / EEEZ MF 172.18 241.5 MW 391.42
MF C7H13N3O3 MF C H ClNO 11 12 3 MF C18H25N5O5
Step II
CH3 CH3 CH3 H3C O HO O O N N N CH3 O 2 H C CH3 2H O (NH OH) H SO H C CH 2 3 + 2 + 2 2 2 4 2 3 3 OH H2SO4 2H O H3C + + + 2 N N O O OH CH3 MF C5H12O2 CH3 BOK-EE/EZ/ZE BOO-EZE/EZZ/EEE MW 258 MW 172.18 MF C H N O MF C H N O 12 22 2 4 7 12 2 3
M/s. PI Industries Ltd. 104
Step III
CH3 CH3 HO O O O N N Cl N N O O 2CH OH NaCl CH ONa O O CH NH H3C CH3 N CH 3 + H3C CH3 3 + 3 2 3 + + + N CH3 N N N O O H O H C H3C 3 CH3 CH3 BOO-EZE/EZZ/EEE CLMO ORST-EEEE / EEEZ MF 172.18 241.5 MW 391.42 MF C H N O 7 13 3 3 MF C11H12ClNO3 MF C H N O 18 25 5 5
Mass Balance:
Mass balance of ORST (Orysastrobin) Kg Kg MIPD-Ketal 366 1060 Effluent to MEE NaOH 100 Formation of BOK Methoxy Amine 723 hydrochloride
DM Water 581 625 Effluent to ETP Formation of BOO Hydroxylamoniumsulfate 890 500 H2SO4 Byproduct
Sodium Mithylate 72 608 Effluent to ETP CLMO 310 Formation of 1000 ORST Methylamine 119 methylamide DM Water 633
Total 3794 3794
M/s. PI Industries Ltd. 105
49. (RS)-3, 5-Dichloro-N-(3-Chloro-1-Ethyl-1-Methyl-2-Oxopropyl)-p- Toluamide Manufacturing Process:
Step-1 3-methyl, 1-pentyne-3-ol reacts with Phosphoryl Chloride forms mass of 3-Chloro-3-Methyl-1- pentyne. Step-2 Along with Ammonia gas under Amination reaction, 3-Chloro-3-Methyl- 1- pentyne forms 3-Amino-3-Methyl-1-pentyne. Step-3 Methyl p-toluene and chlorine gas forms Methyl-3, 5-dichloro-4- methylbenzoate. Step-4 Mehtyl-3, 5 -dichloro-4-methylbenzoate along with hydrochloric acid and sodium chloride forms 3 ,5-dichloro-4-methyl benzoic Acid form. Step-5 3, 5-dichloro-4-methyl benzoic Acid along with thionyl chloride forms 3, 5-dichloro-4-methyl benzoyl chloride derivatives. Step-6 3, 5-dichloro-4-methyl benzoyl chloride and 3-amino 3-mehtyl 1- pentane together reacts with each other and charge with MIBK to forms 3, 5- dichloro-4-methyl benzoyl chloride solution in MIBK. Step-7 3, 5-Dichloro-4-Methyl Benzoyl Chloride solution in MIBK reacts in presence of silver nitrate to form Methyl 3,5-Dichloro-4-Methyl Benzoic acid in MIBK. Step-8 Methyl 3, 5-Dichloro-4-methyl benzoic acid in MIBK is treated with TCIA powder then given caustic wash and water wash to form MIBK Solution of Zoxamide. Step-9 MIBK Solution of Zoxamide is given water wash to remove MIBK and drying process carried out to get dry ZXMD. Chemical Reaction:
Step I
Cl OH H3C H PO H3C POCl + 3 4 + 3 H3C CH H3C CH
Phosphoryl chloride 3-Chloro-3-Methyl-1-pentyne 3-Methyl-1-pentyne-3-ol
M/s. PI Industries Ltd. 106
Step II Cl NH2 H C Amination 3 2 NH CH3 3 H3C NH Cl + + 4 CH3 CH Ammonia gas CH 3-Chloro-3-Methyl-1-pentyne 3-Amino-3-Methyl-1-pentyne
Step III Cl COOCH COOCH 3 3
2 Cl2 + 2 HCl + H3C H3C Cl Hydrochloric acid Chlorine gas Methyl-p-toluate methyl 3,5-dichloro-4-methylbenzoate
Step IV
Cl COOCH3 Cl COOH
+ HCl + NaOH + NaCl + CH OH 3 H3C H3C
Cl Cl
methyl-3,5-dichloro- 3,5-dichloro-4-methylbenzoic acid 4-methylbenzoate
Step V
Cl COOH Cl COCl
SOCl2 SO HCl + + 2 + H3C H3C Cl Cl Thionyl chloride 3,5-dichloro-4-methyl 3,5-dichloro-4-methyl benzoic acid benzoyl chloride
Step VI
CH3 O NH2 Cl COCl CH3 MIBK Cl H3C NH + CH3 + HCl H3C CH H3C Cl CH Cl 3,5-dichloro-4-methylbenzoyl chloride 3-Amino-3-Methyl-1-pentyne 3,5-dichloro-4-methyl benzoyl chloride solution in MIBK
Step VII CH 3 H3C O CH3 CH3 N Cl AgNO3 NH Cl CH2 O CH H3C H3C Cl Cl 3,5-Dichloro-4-methyl benzoic acid in MIBK methyl 3,5-Dichloro-4-methyl benzoic acid in MIBK
M/s. PI Industries Ltd. 107
Step VIII H C H C 3 3 CH CH N 3 N 3 Cl Cl CH2 O O NaOH Cl
TCIA H3C H3C Cl Cl
methyl 3,5-Dichloro-4-methyl benzoic acid in MIBK MIBK solution of Zoxamide
Step IX
H3C CH CH3 N 3 O CH Cl Cl 3 O NH Cl + H2O O Cl H3C H3C Cl Cl ZXMD MIBK solution of Zoxamide
Mass Balance:
M/s. PI Industries Ltd. 108
Mass balance of ZXMD (Zoxamide) Kg Kg Stage-I 3-Methyl-1-pentyne-3-ol 559 Formation of 79 Effluent to MEE intermediate-1 POCl3 581
Ammonia 303 491 Effluent to MEE Formation of 3-Amino-3-methyl-1- intermediate-2 874 pentyne
Stage-II Methyl-p-Toluate 437 Formation of 361 HCl by-product Chlorine gas 245 intermediate-3
HCl 96 Formation of 98 Effluent to ETP NaOH 110 intermediate-4
Thionyl Chloride 662 117 Effluent to MEE SO2 + HCl spent to Formation of 129 scrubber Intermediate-5 3,5-dichloro-4-methyl 844 benzoyl chloride
3,5-dichloro-4-methyl benzoyl chloride (Stage- 844 793 HCl By-product II) Formation of MIBK 572 Intermediate-6 680 Effluent to MEE 3-Amino-3-methyl-1- 874 561 MIBK Recovery pentyne (Stage-I)
AgNO3 1 Formation of 113 Effluent to ETP Water 492 Intermediate-7
TClA 162 205 Effluent to ETP Formation of NaOH 46 Intermediate-8 Water 532
Water 205 376 Effluent to ETP Formation of Step-9 1000 ZXMD
Total 6720 6720
M/s. PI Industries Ltd. 109
50. 3, 4, 5-Trifluoro-aminobiphenyl
Manufacturing Process:
Magnesium and THF is added to AAA BrT FB raw material forming AAA-Mg Br which is further reacted with trimethoxy boron in presence of THF forming intermediate mixture of AAA – Boronic Ester and agitating the same mixture for a while gives final product AAA-Boronic Acid (AMB) Chemical Reaction:
+ OCH3 MgBr H CO OCH MgBr H CO 3 3 Br 3 - B H3CO B OCH3 B OCH3 MW: 103.9 Mg H3CO THF THF + F F F F F F F F F F F F AAA-BrT AAA-Mg HCl / H2O AAA-Boronic FB Br MW: 339.21 ester MW: 210.979 MW: 235.284 HO OH MW: 203.96 B
Mg(Br)(Cl) + + 3 CH3OH F F + H2O F AAA-Boronic acid MW: 175.9
Mass Balance:
Mass balance of AMB (3,4,5-Trifluoro-aminobiphenyl) Kg Kg Magnesium turnings 15 522 Effluent to ETP Dry THF 664 644 THF recycled AAA-BrTFB 967 264 Residue to incinerator B(OCH3)3 531 Formation of AMB 531 Effluent to MEE HCl 22 1000 AMB Water 676 Caustic lye 86
Total 2961 2961
M/s. PI Industries Ltd. 110
51. S-Benzyl O, O-DiIsopropyl Phosphorothioate
Manufacturing Process:
SDTP and Benzyl Chloride reacted with toluene forms KTZ (Kitazin).
Chemical Reaction:
(CH ) CHO 3 2 O (CH3)2CHO O Cl Toluene P P + + NaCl (CH3)2CHO SNa (CH3)2CHO S
SDTP Benzyl Chloride KTZ MW 220.2 MW 126.59 MW 288.35
Mass Balance:
Mass balance of KITAZIN Kg Kg SDTP 1130 750 Effluent to MEE Toluene 254 248 Rec. Toluene Benzylchloride 444 Kitazin 25 Reside to incinerator Water 768 572 Effluent to ETP 1000 Kitazin
Total 2595 2595
M/s. PI Industries Ltd. 111
52. 2-[3-Chloro-5-(Trifluoromethyl) Pyridin-2-yl] Ethanamine
Manufacturing process:
Step-1 2,3–dichloro-5-(trifluoromethyl) pyridine, Ethylcyno acetate, Potasium Hydroxide and Hydrochloric acid are agitated in a reactor to form [3-Chloro-5- (trifluoromethyl) pyridine-2-yl ]acetonitrile Step-2 Dimethyle Ethar with charging of Hydrogen gas forms N-{2-[3-chloro-5- (trifloromethyl) pyridine-2-yl] ethyl} acetamide. Step–3 Just the solution of HCl is added to above mention intermediate to form final product CTPE. Chemical Reaction:
Step I
F3C F3C N NC NMP N OEt KOH HCl CN CO EtOH KCl 2H O Cl + + + + 2 + + + 2 O Cl Cl 2,3-dichloro-5-(triflu (ethyl [3-chloro-5-(trifluoromethyl) oromethyl)pyridine cyanoacetate) pyridin-2-yl]acetonitrile
Step II
F C F C 3 N 3 N O H2 CH COOH CN + 2 H + (CH3CO)2O + 3 AcOH NH Cl Cl N-{2-[3-chloro-5-(trifluoro [3-chloro-5-(trifluoromethyl) methyl)pyridin-2-yl]ethyl} pyridin-2-yl]acetonitrile acetamide
Step III F F3C N O c. HCl F N CH COOH H O F + 3 NH + 2 NH2 Cl Cl N-{2-[3-chloro-5-(trifluoro methyl)pyridin-2-yl]ethyl} (CTPE) acetamide
M/s. PI Industries Ltd. 112
Mass Balance:
Mass balance of CTPE Kg Kg 2,3 dichloro-5- trifluoromethyl) 659 320 CO2 to Scrubber pyridine NMP 2511 10 H2 to atmosphere Formation of Step 1 KOH 64 713 Effluent to MEE ethyl acetoacetate 693 2270 Distillate recovery Water 380 HCl 596
Acetic anhydride 275 935 Distillate recovery Acetic acid 430 Formation of Step 2 Hydrogen 10
Water 780 1160 Effluent to ETP Residue to HCl 290 Formation of Step 3 280 incinerator 1000 CTPE
Total 6688 6688
M/s. PI Industries Ltd. 113
53. Methyl (E)-2-{2-[6-(2-Cyanophenoxy) Pyrimidin-4-yloxy] Phenyl}- 3-Methoxyacrylate Manufacturing Process: Step-1 Acetic anhydride and Trimethyorthoformate is reacted and agitated with 2-(3H) Benzofuranone to form intermediate 3-(Methoxymethylene) benzofuran 3(H)-one. Step-2 4, 6 Dichloropyrimidine and sodium methanoate is added in the intermediate to form (E) Methl-2[2-(6-chloropyrimidine-4-yl-oxy) phenyl] -3- methoxypropanoate. Step-3 (E) Methl-2[2-(6-chloropyrimidine-4-yl-oxy) phenyl] -3- methoxypropanoate is further agitated with 2 Cynophenol and DMF or K2CO3 to form final product. Chemical Reaction: CH 3 O Step-1st O Acetic Anhydride O 2 CH O + 3 Trimethyorthoformate O
2-(3H)-Benzofuranone 3-(Methoxymethylene)benzofuran-3(H)-one
Cl Cl
Step-2nd N N NaOMe 4,6-Dichloropyrimidine
OH CN O O H C CH 3 O O 3 H C CH CN 3 O O 3 2-Cyanophenol Cl O O O NaCl N N + N N Step-3rd (E)-MEthl-2[2-(6-chloropyrimidin-4yl-oxy)phenyl]- DMF / K2CO3 AZST 3-methoxypropenoate
+ KCl + CO2 + H2O
M/s. PI Industries Ltd. 114
Mass Balance: Mass balance of AZST(methyl (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3- methoxyacrylate) Kg Kg 2(3H)-Benzofuranone 482 697 Effluent to MEE Trimethyl orthoformate 686 Formation of 162 Effluent to ETP Acetic anhydride 708 intermediate-1 47 Filtered solid to incinerator Water 774 672 Trimethyl to recovery
sodium methoxide 441 77 Filtered solid to incinerator Formation of 4,6-Dichloropyrimidine 577 892 Effluent to MEE intermediate-2 180 Residue to incinerator
2-cynophenol 238 123 Filtered solid to incinerator Formation of AZST, Potessium carbonate 4 489 Rec. DMF Crystallisation, DMF 500 571 Effluent to ETP Filtration and drying Water 500 1000 AZST
Total 4910 4910
M/s. PI Industries Ltd. 115
54. 4-(Methoxy-6-(Trifluoromethyl)-1, 3, 5-Triazin-2-Amine Manufacturing Process: 3-Amino-1, 2, 4-triazole is reacted with Methanol and Nitroimidazole to form CMTH. Chemical reaction:
O O NH N N 2 F F N MeOH O CF3COONa 2 CH3OH + + F NaOMe, H O F + + H2N NH F 2 H2N N F C H N C H F O 2 4 4 CH4O 3 3 3 2 C5H5F3N4O
Mass Balance: Mass balance of CMTH Kg Kg Methyl 575 449 Methanol recovered trifluoroacetate Methanol 462 265 Effluent to ETP Formation of Step-1 2-Cyanoguanidine 80 1000 CMTH Sodium methoxide 360 Water 235
Total 1714 1714
M/s. PI Industries Ltd. 116
55. (1RS, 2SR, 5RS; 1RS, 2SR, 5SR)-2-(4-Chlorobenzyl)-5-Isopropyl-1- (1H-1, 2, 4-Triazol-1-ylmethyl) Cyclopentanol Manufacturing Process: Step-1 Dimethyl hexanediotate treated with sodium methanoate and Toluene or DMF to form Ketone Intermediate. Step-2 Ketone Intermediate reacts with toluene forms Methyl 1-(4- chlorobenzyl)-2-oxocyclopentanacarboxylate. Step-3 Methyl 1-(4-chlorobenzyl)-2-oxocyclopentanacarboxylate rearrangement reaction done in presence of sodium methanoate or DMF, forms C14H14ClNaO3. Isopropylation of the same compound with IPB or KI or DMF adds the ethyl group in the structure. Followed by Hydrolysis and Decarboxylation forms 2-(4- chlorobenzyl)-5-isopropylcyclopentanone (Ketone-IP)
Step-4 Ketone-IP treated with TMSOB forms C16H21ClO. This compound treated with sodium salt forms IPCZ. Chemical Reaction:
Step I
Na Cyclisation:- O
COOMe MeONa COOMe 2 Tol / DMF + COOMe dimethyl hexanedioate
Benzylation:-
Cl O Na O Cl COOMe COOMe
Toluene Cl + NaCl
M/s. PI Industries Ltd. 117
Step II
Rearrangement Reaction:-
O Na COOMe O DMF Cl COOMe MeOH NaOMe + Cl +
methyl 1-(4-chlorobenzyl)-2-oxocyclop entanecarboxylate
Isopropylation Reaction:- Na O O CH3 Cl COOMe KI/DMF IPB Cl + CH3 NaBr COOMe +
methyl 3-(4-chlorobenzyl)-1-isopropyl-2- oxocyclopentanecarboxylate
Hydrolysis - Decarboxylation:-
O CH3 O CH3 Cl Cl CH3 NaOH/Toluene CH Na CO + 3 + MeOH+ 2 3 COOMe
(Ketone-IP) 2-(4-chlorobenzyl)-5-isopropylcyclopentanone
Step III
O CH3 CH Cl TMSOB / t-BuONa / NMP O 3 CH3 Cl CH3
(Ketone-IP) 4-(4-chlorobenzyl)-7-isopropyl-1-oxaspiro[2.4]heptane 2-(4-chlorobenzyl)-5-isopropylcyclopentanone
H3C CH3
M/s. PI Industries Ltd. 118
N
H3C CH3 Na N N O CH3 Sodium salt of 1H-1,2,4-triazole Cl CH3
N
N N HO CH3 Cl
CH3
(IPCZ) 2-(4-chlorobenzyl)-5-isopropyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol
Mass Balance:
M/s. PI Industries Ltd. 119
Mass Balance of IPCZ Kg Kg Toluene 689 146 Methanol Recovery Dimethyl Adipate 1177 655 Toluene-recycled Sodium Methoxide 397 Cyclyzation and DMF 98 Benzylation reaction of IPCZ p-chlorobenzyl chloride 1050 Water 1261
Sodium Methoxide 397 188 Methanol Recovered Rearrangement Toluene 1204 896 DMF Recovered reaction of IPCZ DMF 933
Potassium Iodide 45 4121 NaBr By-product Isopropylation Isopropyl Bromide 884 reaction of IPCZ Water 450
Sodium Hydroxide 67 1741 Recovered Toluene Toluene 1795 1397 Effluent to MEE Water 1171 581 Methanol Recovered Decarbonation 612 Effluent to ETP reaction of IPCZ 749 Effluent to Incinerator
139 Residue to Incinerator
Sodium salt of 1,2,4- 766 1138 N-methyl pyrrolidone Triazole N-methyl pyrrolidone 1185 966 Effluent to MEE Sodium tert-butoxide 442 167 LOD to incinerator Formation of IPCZ TMSOB 1596 899 Effluent to ETP Water 111 321 Effluent to Incinerator 1000 IPCZ
Total 15716 15716
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56. 1-(2-Fluorophenyl)-1-(4-Fluorophenyl)-2-(1, 2, 4-Triazol-1-yl) Ethanol Manufacturing Process: 2-(2-florophenyl)-2-(4-fluorophenyl) oxirane when reacts with 1, 2, 4-triazol
and K2CO3 with DMF forms Flutriafol.
Chemical Reaction:
O HO N N DMF N N + + K2CO3 N N K2CO3 F + F F H F 1,2,4-Triazole 2-(2-fluorophenyl)-2-(4 Flutriafol MW 138.2 -fluorophenyl)oxirane
Mass Balance: Mass balance of FTL Kg Kg DMF 741 507 Effluent to MEE 1,2,4-Triazole 371 384 Effluent to ETP Potassium carbonate 17 Formation of Step 1 248 LOD to incinerator FOX 1153 711 DMF recovery Water 568 1000 FTL
Total 2850 2850
M/s. PI Industries Ltd. 121
57. 2-(2-fluorophenyl)-2-(4-fluorophenyl)-oxirane Manufacturing Process: Step-1 2-Florobenzoyl Chloride and fluorobenze are treated with each other in a closed reactor forms 2, 4-Difluorobenzophenone. Step-2 2, 4 Difluorobenzophenone is further treated with KOH, dimethyl sulphate and DABCO along with toluene to form FOX. Chemical reaction:
Step I
F O F Cl + + HCl O F F 2-Fuorobenzoyl 2,4'-Difluorobenzophenone chloride Fuorobenzene
Step II O O O KOH, DABCO O S KOH H O + O + + KCH3SO4 + 2 O F F Toluene F F
2,4'-Difluorobenzophenone 2-(2-fluorophenyl)-2-(4-fluoro phenyl)-oxirane (FOX)
Mass Balance: Mass Balance of FOX Kg Kg 2-fluorobenzoyl Chloride 564 271 HCl By-Product Fluorobenzene 304 Formation of Step 1 Aluminium Chloride 255
dimethyl sulfoxide 806 401 Recovered toluene dimethyl sulphate 521 549 Effluent to ETP KOH 77 591 Effluent to MEE Dimethyl sulfoxide DABCO 23 Formation of Step 2 765 recovery Water 616 1000 FOX Toluene 412
Total 3577 3577
M/s. PI Industries Ltd. 122
58. (4-Chlorophenyl) Methyl N-(2,4-Dichlorophenyl)-1H-1,2,4-Triazole- 1-Ethanimidothioate Manufacturing Process:
Step-1 2, 4-dichloro aniline and chloroacetyl chloride treated with Na2CO3 and Toluene, forms IMB-A1. This on further reaction with Toluene and PCl5 forms IMB-A2 Step-2 1-chloro-4-(chloromethyl) benzene and Thiourea agitated with water forms 4-chlorobenzyl imido thaio carbamate hydrochloride, which is further treated with NaOH forms Intermediate. Addition of HCl after the reaction completes, forms IMB-B
Step-3 C8H5Cl4N reacts with triazole forms amine derivative which is further treated with Toluene and IMB – B to forms IBCZ Chemical Reaction: Step I
Cl O Cl Cl O Na2CO3/ Toluene + Cl NH + Cl NH2 HCl Cl Cl chloroacetyl chloride 2,4-dichloroaniline 2-chloro-N-(2,4-dichlorophenyl)acetamide Mol. F. = C H Cl N 6 5 2 Mol. F.= C2 H2 Cl2 O Mol. F.= C8 H6 Cl3 N O IMB-A1 Toluene PCl5
Cl Cl Cl
Cl N
(1Z)-2-chloro-N-(2,4-dichlorophenyl)ethanimidoyl chloride Mol. F.= C H Cl N 8 5 4 IMB-A2
M/s. PI Industries Ltd. 123
Step II NH
+ H2O Cl (NH2)2CS S NH2 Cl Cl 1-chloro-4-(chloromethyl)benzene 4-chlorobenzyl imidothiocarbamate Hydrochloride
Mol. F. C H Cl 7 6 2 NaOH / H2O
HCl NH2 + Cl Cl O NH SH S Na 2 (4-chlorophenyl)methanethiol urea
Mol. F = C H Cl S IMB-B 7 7
Step III N N N N N N N N Cl Cl Cl N H Cl N 1H-1,2,4-triazole Cl N Cl
Mol. F.= C8 H5 Cl4 N Cl N-(2,4-dichlorophenyl)-N-[(1Z)-1,2-di-1H-1,2,4-triazol-1-ylethylidene]amine Cl
CH3CN / Toluene S Cl Cl N SH N N IMB-C N 4-chlorobenzyl (1Z)-N-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanimidothioate
Mol. Formula = C17 H13 Cl3 N4 S
Mass Balance:
M/s. PI Industries Ltd. 124
Mass Balance of IBCZ ((4-chlorophenyl)methyl N-(2,4-dichlorophenyl)-1H-1,2,4- triazole-1-ethanimidothioate)) Kg Kg Stage-I 2,4-dichloroaniline 358 538 Recycled Toluene Chloro Acetyl Chloride 345 311 Effluent to ETP Sodium Carbonate 43 Formation of 692 Intermediate-1 Phosphorous intermediate-1 240 pentachloride Toluene 555
Stage-II 1-Chloro-4- 405 721 Effluent to ETP (chloromethyl) benzene Formation of CS.(NH2)2 220 655 Intermediate-2 intermediate-2 HCl 35 NaOH 114 Water 602
1,2,4-Triazole 232 184 Toluene -recycle Intermediate-1 (Stage-I) 692 1121 Effluent to MEE Cyanomethane Intermediate-2 (Stage-II) 655 331 Formation of IBCZ recycle Cyanomethane 338 1000 IBCZ Water 531 Toluene 188
Total 5553 5553
M/s. PI Industries Ltd. 125
Fine Chemicals 59. 2-Amino-3-Chlorobenzoic Acid Methyl Ester Manufacturing Process: Step-1 Ammonia gas along with MeOH agitated in reactor to form an intermediate product 3-CAA
Step-2 3-CAA then treated with K2CO3 and TBAB to form ACBM final Product.
Chemical Reaction:
Step I
O OH O OH NH3 / MeOH CuCl (cat.) Cl 2 NH NH2 + + NH4Cl
Cl Cl (DCBA) (3-CAA)
Step II O OH O O O K CO , TBAB NH 2 3 O 2 O S O + NH2 + O S O O MIBK Cl OH Cl
(3-CAA) (ACBM) Mass Balance: Mass Balance of ACBM Kg Kg 2,3 dichloro benzoic LOD to 638 50 acid incinerator copper chloride 4 Formation of Step 1400 Effluent to MEE ammonia 571 1 Water 664 hydrochloric acid 53
MIBK 1360 1333 recovered MIBK Dimethyl Sulphate 144 394 Effluent to ETP Formation of Step TBAB 108 1000 ACBM 2 pottassium carbonate 4 Water 630
Total 4177 4177
M/s. PI Industries Ltd. 126
60. 5-Amino-1, 2, 4-Triazole-3-Thiol Manufacturing Process: Aminoguanidine bicarbonate is agitated with Ammonium thiocyanate forms intermediate hydrazine carboximidamide. HCl is added further to this intermediate to form 2-carbamimidoyl hydrazine carbothioamide. Then NaOH is mixed with this to produce final product 5-amino1, 2, 4 triazole-3-thiol (AMT). Chemical Reaction: NH NH CO2 H2N NH + 3 + H N NH4SCN 2 NH NH NH .H2CO3 + 2 HSCN NH2 Aminoguanidine bicarbonate Ammoniumthiocyanate hydrazinecarboximidamide F.W =133.17 F.W =136.10 F.W =76.12 HCl
H NH N NaOH NH S N NH2 H2N H2O + NH4Cl + NH HCl N NH2 HS 2-carbamimidoylhydrazinecarbothioamide 5-amino-1,2,4-triazole-3-thiol F.W =169.63 (AMT)
F.W =116.14
Mass Balance:
Manufacturing process of AMT Kg Kg Aminoguanidine 570 600 Effluent to MEE Bicarbonate Ammonium 510 365 Effluent to ETP Thiocynate Formation of Step 1 Water 880 84 LOD to incinerator HCl 42 1000 AMT Caustic Soda 47
Total 2049 2049
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61. 1-(Tetrahydropyran-4-yl) Ethanone Manufacturing Process: Step-1 Methyl aceto acetate and DMF is agitated with Bis (2-Chloroethyl) ether to form ATHC mixture as intermediate.
Step-2 This Intermediate is further dissolved in aqueous H2SO4 solution form final Product ATHP. Chemical Reaction: Potassium Iodide O O O Potassium carbonate O + K2CO3 + KCl KI Cl Cl + O + O DMF O Bis(2-chloroethyl)ether Methyl acetoacetate O ATHC O O O O Aq. H SO 2 4 + H2SO4 Sodium bicarbonate + H CH O O 3 EDC methyl formate Sulphuric acid O O
ATHC ATHP
Mass Balance: Mass Balance of ATHP Kg Kg Bis dichloro 1096 1639 DMF recycled diethylether Residue to DMF 1707 259 incinerator Potassium Formation of ATHC Solid to 99 93 carbonate incinerator Potassium Iodide 22 Methyl 599 Acetoacetate
H2SO4 192 1083 Effluent to ETP DM Water 555 984 EDC recycled Sodium Formation of ATHP Residue to 5 222 bicarbonate incinerator EDC 1004 1000 ATHP
Total 5280 5280
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62. 4-Chloro-2, 6-Dimethyl Aniline Manufacturing Process:
Chlorination of 2, 6- Dimethyl Aniline with H2SO4, EDC NaOH will produce CDMA. Chemical Reaction:
NH NH2 2 i) EDC H SO Cl Cl + 2 4 + HCl Na2SO4 2H2O ii) 2 NaOH + + +
Cl 2,6-dimethylaniline (CDMA)
Mass Balance: Mass Balance of CDMA Kg Kg 2,6-Dimethylaniline 990 236 HCl Recovered EDC 1580 880 Effluent to MEE Sulphuric Acid 778 530 Effluent to ETP Caustic 25 1533 Distilled EDC recovered Formation of Step 1 Chlorine Gas 194 124 Distilled DMA recovered Water 737 1000 CDMA
Total 4303 4303
M/s. PI Industries Ltd. 129
63. 4-Chloro 2, 6-Dimethyl-Bromo Benzene Manufacturing Process:
Step-1 2, 6 – Dimethyl aniline and H2SO4 is chlorinated in a reactor by adding the chlorine gas in presence of EDC produce CDMA bisulfate salt.
Step–2 The Salt is further reacted with NaNO2 along with Hydro bromide produce CDMB Chemical Reaction:
- + HSO Step I NH3 4 NH2
+ H2SO4 + Cl Cl HCl EDC +
Cl 2,6-dimethylaniline CDMA (bisulfate salt)
Step II + NH - Br 3 HSO4
NaNO NaBr + 2 + HBr + N2 +
Cl Cl
CDMA (bisulfate salt) CDMB
Mass Balance:
Mass Balance of CDMB Kg Kg EDC 1353 760 HCl by-product 2,6-Dimethyl Aniline 593 1312 Recovered EDC Formation of Step 1 Sulphuric Acid 585 Chlorine Gas 625
Hydrobromic Acid 189 661 Effluent to MEE Sodium Nitrite 597 732 Effluent to ETP N2 Gas to Wet Water 822 242 Formation of Step 2 scrubber Residue to 57 Incinerator 1000 CDMB
Total 4764 4764
M/s. PI Industries Ltd. 130
64. 1-Cyclopropy-2(2fluorophenyl) Ethanone Manufacturing Process: Isopropyl chloride and magnesium metal forms Isopropyl Magnesium chloride. This solution is further reacted with 2-Floro Toluene to form an Intermediate. The intermediate is further treated with CPCM and hydrochloric acid to form CPFK. Chemical Reaction:
H C CH H3C CH3 3 3 + 2 + Mg Cl MgCl Isopropyl chloride Magensium Metal Isopropyl magensium chloride
F F H3C CH3 + CH3 + Mg --Cl H3C
MgCl CH3 Isopropyl magensium chloride 2-Fluoro Toluene Propane
F O F CH OH 2MgCl + + 2HCl O + 3 + 2 H CO Mg --Cl 3 Methanol Magenisum Chloride CPCM Hydrochoric acid CPFK
+2 CO2 Carbondioxide Mass Balance: Mass balance of CPFK Kg Kg Magnesium 38 Turnings Formation of Step-1 2-Chloropropane 2450
Propane Gas 2-Fluoro Toluene 521 Formation of Step-2 42 incineration
CPCM 460 606 Effluent to MEE HCl 102 1661 HCl by-product Methanol Formation of CPFK DM Water 680 601 Recovered 340 Effluent to ETP 1000 CPFK
Total 4250 4250
M/s. PI Industries Ltd. 131
65. N, N'-Bis(2-Hydroxyethyl) Ethylene Diamine Manufacturing Process: Ethylene diamine treated with 2-chloroethanol in presence of sodium carbonate forms the product. Chemical Reaction:
Cl NH NH2 OH H2 N 2 OH Na2CO3 HO NH + + H O CO + 2 NaCl + 2 + 2 Ethylenediamine 2-chloroethanol Sodium DAEEA carbonate Sodium chloride
Mass Balance:
Mass balance of DAEEA Kg Kg Ethylene Diamine Ethylene Diamine 1498 1438 Recovered 2-Chloro Ethanol 1344 503 Effluent to MEE Formation of DAEAA Sodium Carbonate 7 554 Effluent to ETP DM Water 646 1000 DAEEA
Total 3495 3495
M/s. PI Industries Ltd. 132
66. 2, 3- Dichloro-5-(Trichloromethyl) Pyridine Manufacturing Process:
Step-1 Nicotinic Acid is react with chlorine gas and PCl3 in auto clave to form 2, 3-dichloro-5-(trochloromethyl pyridine). Step – 2 2, 3-dichloro-5-(trichloromethyl) pyridine treated with hydrogen fluoride in auto clave to form final product 2, 3-dichloro-5-(trifloromethyl) pyridine (DCTFP). Chemical reaction:
Step Step Cl F O F Autoclave Cl Autoclave Cl Cl + POCl3 3 Cl PCl HF HO 3 Cl F + 3 + HCl H2O N Cl + N N Cl 2,3-dichloro-5-(trichloromethyl) 2,3-dichloro-5-(trifluoromethyl)pyridine Nicotinic acid pyridine
Mass Balance:
Mass balance of DCTFP Kg Kg Phosphorous 1549 120 HCl By-product Trichloride Formation of Step Nicotinic Acid 347 1494 Distilled recovered 1 Chlorine 528 183 Effluent to MEE Water 483
AHF 565 844 Effluent to ETP Formation of Step Water 524 355 HCL by-product 2 1000 DCTFP
Total 3996 3996
M/s. PI Industries Ltd. 133
67. 2, 2-Dimethyl-5-Hydroxymethyl-1, 3-Dioxane Manufacturing Process: Step-1 Ethanol, Sodium pieces and p-Formaldehyde are reacted together with Diethylmalonate which form a mass. This mass is treated with Sulphuric acid there by producing the first intermediate DHM. Step-2 The intermediate obtained in 1st step is treated with Triethyl Ortho Formate successively thrice and addition of Acetone thereafter gives the intermediate product DDD. Step-3 Dimethyl sulfoxide, Water and Sodium Chloride are charged in the above mass and agitated producing another intermediate DCD. Step-4 The above intermediate is treated with a mixture of Diethyl Ether, Lithium Aluminum Hydride. Adding water and ether to the reaction mass gives the crude form of DHD. The crude mass is then distilled to obtain final product DHD. Chemical Reaction: Step I
COOC2H5 HO COOC2H5 2 + CH2O
COOC2H5 HO COOC2H5
Diethylmalonate DHM
Step II O HO COOC2H5 COOC2H5 CH(OC H ) 2 C H OH + 2 5 3 H5C2O + 2 5 COOC2H5 O HO COOC2H5
DHM TEOF DDD Int DDD Int
O O O H C COOC H COOC2H5 3 2 5 H5C2O HCOOC H + H3C CH3 + 2 5 COOC2H5 H3C COOC2H5 O O
DDD Int Acetone DDD
M/s. PI Industries Ltd. 134
Step III
O H3C COOC2H5 O DMSO H C + H2O 3 H3C COOC2H5 COOC2H5 C2H5OH CO2 O + + H3C O
DDD DCD
Step IV
O O H3C H3C COOC H LiAlH CH OH C H OH LiOH Al(OH) 2 5 + 4 2 + 2 5 + + 3 + 2H2 H3C H3C O O 4H2O LAH DCD DHD
Mass balance: Mass balance of DHD Kg Kg Methanol 918 895 Methanol-recovered Paraformaldehyde 628 Formation of Step 1 239 Residue to incinerator Diethylmalonate 1522
Triethyl Ortho Formate 888 818 Effluent to MEE Sodium Bisulphate 108 678 Acetone recovery Acetone 714 Formation of Step 2 339 Recovered Toluene Toluene 346 Water 150
Dimethyl sulfoxide 829 250 CO2 Sodium chloride 440 575 Effluent to MEE Formation of Step 3 Dimethyl sulfoxide Toluene 522 1354 recovery Water 261 512 Recovered Toluene
Lithium aluminium Hydrogen gas to 265 93 hydride atmosphere KOH 20 317 Effluent ETP Formation of Step 4 Solid to solid Water 431 754 Incinerator 219 Residue to Incinerator 1000 DHD
Total 8043 8043
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68. 4, 4-Dimethoxy-2-Butanone
Manufacturing Process: Step-1 Methyl Formate charged with sodium methoxide and methyl formate forms Sodium Formyl Acetone.
Step-2 Sodium Formyl acetone is further treated with methanol and H2SO4 and the methanol is added slightly along the wall of the reactor in reaction. Agitation of the mass gives the final product DMB. Chemical Reaction:
Step I O O - O O CH + + NaOCH3 2 CH H O MeOH + ONa + 3 O Na
(Methyl formate) (Sodium formyl acetone)
Step II O O O 2 CH H SO NaHSO H O ONa + 3 + 2 4 + 4 + 2 MeOH O
(Sodium formyl acetone) (DMB)
Mass balance: Mass balance of DMB Kg Kg Wet cake to Methanol 851 717 incineration Water 698 347 Effluent to MEE Formation of Step 1 Methyl formate 905 834 Methanol Recovered Acetone 640 NaOCH3 349
Wet cake to Methanol 2553 188 Incineration Water 397 703 Effluent to ETP H2SO4 123 Formation of DMB 2489 Methanol recycled Residue to 238 Incineration 1000 DMB
Total 6516 6516
M/s. PI Industries Ltd. 136
69. 2-Ethyl-2-Methyl Butanoic Acid Manufacturing Process: Step-1 Propionitrile and Ethyl Bromide treated with sodamide in presence of THF forms 2-Ethyl 2-Methyl Butyronitrile.
Step-2 2-Ethyl 2-Methyl butyronitrile reacts with water and H2SO4 to form final product Ethyl Methyl Butanoic Acid (EMBA) Chemical Reaction:
Step I
H C H3C CH3 3 THF 2 N 2 H3C Br+ Na NH2 + N + 2NaBr + 2NH3 H3C Propionitrile Ethyl bromide Sodamide 2-Ethyl-2-methyl butyronitrile
Step II
COOH H3C CH3 2 H OH H C CH NH3 N + 3 3 + H3C H2SO4 H C 2-Ethyl-2-methyl butyronitrile 3
2-Ethyl-2-methylbutanoic acid Mass Balance:
Mass balance of EMBA Kg Kg Sodamide 583 1701 Recovered THF Propionitrile 324 236 NH3 by-product Ethyl Bromide 809 872 Effluent to MEE Formation of Step-1 Effluent to Water 339 310 Incinerator THF 1727
Sulphuric Acid 553 739 Effluent to ETP Residue to Water 658 49 Formation of EMBA incinerator 86 NH3 By-product 1000 EMBA
Total 4993 4993
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70. Mono Methyl Hydrazine Manufacturing Process: Hydrazine Hydrate treated with Methyl chloride with NaOH forms MMH. Chemical Reaction: NaOH Cl CH3 H O H2N NH2 NaCl + 2 + H3C H2N NH +
Hydrazine Methylchloride MMH hydrate
Mass Balance: Mass balance of MMH Kg Kg Chloroform 1548 861 Residue to Incinerator Hydrazine Hydrate 1501 499 Effluent to ETP Caustic Lye 1116 Formation of Step 1 1909 UDMH Water 1331 1227 SDMH 1000 MMH
Total 5496 5496
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71. 10-H Phenothiazine Manufacturing Process: Diphenylamine and Sulphur reacts with each other and forms 10H- phenothiazine. Chemical Reaction: S + 2 S + H2S NH N diphenylamine Sulphur H 10H-phenothiazine Hydrogen sulphide gas
Mass Balance: Mass balance of 10-H Phenothiazine Kg Kg H2S Scrubbed in Caustic solution and Diphenylamine 899 178 converted to NaSH byproduct Formation of Step 1 Solid waste to Sulphur 352 63 incineration Water 551 561 Effluent to ETP 1000 10-H Phenothiazine
Total 1802 1802
M/s. PI Industries Ltd. 139
72. 3-Phenoxy Benzaldehyde Manufacturing Process: Step-1 Benzaldehyde along with mixture of bromine and chlorine gas forms MBB. Step-2 MBB with 1, 2 ethenediol in an agitation reaction forms MBBA. Step-3 MBBA and Phenol reacts with each other forms mass which on further reacting with KOH and CuCl forms MPBA.
Step-4 MPBA is dissolved in water and treated with H2SO4 to obtain the product MPB. Chemical Reaction:
Step-I
O H O H O H
2 HCl HBr + Br2 + Cl2 + + +
Cl benzaldehyde Br 3-bromobenzaldehyde 3-chlorobenzaldehyde MBB
Step-II
O O H O OH
+ H2O + OH
Br Br MEG 3-bromobenzaldehyde MBBA
Step-III
O OH O O O CuCl + + KOH + KBr + H2O
Br O phenol MPBA MBBA
M/s. PI Industries Ltd. 140
Step-IV
O O H O OH H2SO4 + O OH + H2O O MEG
MPBA
3-phenoxybenzaldehyde Mass Balance: Mass balance of MPB Kg Kg Benzaldehyde 139 122 HCl by-product Bromine 13 86 HBr By-product Chlorine 46 HCl solution 705 Formation of Step 1 Formic Acid 9 Thio Sloution 357 Soda sloution 7
1,2-Ethanediol (MEG) 1,2-Ethanediol (MEG) 652 Formation of Step 2 403 Recovery
Cuprous chloride 12 357 Effluent to ETP KOH 387 Phenol 605 Formation of Step 3 Water 229 Caustic Lye 185
Water 830 1200 Recovered MEG H2SO4 33 Formation of Step 4 1040 Effluent to MEE 1000 MPB
Total 4208 4208
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Pyrazoles 73. N-{3-Isobutyl-4-[1, 2, 2, 2-tetrafluoro-1-(trifluoromethyl) Ethyl] phenyl}-1, 3, 5- Trimethyl Pyrazole -4- Carboxylic Amide Manufacturing Process: Step-1 IBA and RFI react with each other along with sodium hydrosulfite and potassium carbonate forms intermediates PRFA and ORFA. Step-2 PRFA is then treated with zinc chloride and sodium methoxide, which forms HFMA. Step-3 HFMA and TMC along with NMP and sodium methoxide forms mass of PAN. Step-4 PAN and IBC combine with toluene and sodium hydride forms PFD. Chemical Reaction: Step I
CH3 CH3 CH3 2 Na 2S2O4 CH CH F C 3 3 3 F CH CF 3 3 + F 2 F C 3 I + 2 2 K 2CO 3 + 2 KI + 2 KHCO 3 + 2 Na 2SO 4 + SO2 F3C NH2 NH2 CF NH2 3
F3C F IBA RFI PRFA ORFA
Step II
CH3 CH3 ZnCl2 CH CF CH3 3 F 3 CF CH3 O 3 3 CH3ONa 2 MeOH F3C + NaF + Zn (OH )2 + 2NaCl F3C +
NH2 2 H2O NH2
PRFA HFMA
Step III
H3C CH3 CF O O 3 CH3 CH3 H C CF CH3 3 O F C O 3 NMP 3 H C + 3 N 2 CH OH NaOH F3C CH CH ONa NH CH + 3 + N 3 3 3 H3C NH2 CH3 O H2O N CH3 N H3C
HFMA TMC PAN
M/s. PI Industries Ltd. 142
Step IV
H3C CF H3C O 3 CF O 3 H C F C 3 3 NaH CH3 F3C H3C H3C CH3 H3C NH CH3 + O N NaCl H2 H C + + 3 CH3 O Cl Toluene H C O N CH 3 3 O N CH N 3 H3C N H3C IBC PAN PFD
Mass Balance: Mass balance of PFD Kg Kg Potassium Carbonate 7 256 Salt to Incinerator Sodoium bisulphate 36 33 Effluent to ETP IBA 381 Formation Step-1 482 Ethyl Acetate Recovery Ethyl Acetate 492 RFI 947
Sodium Methoxide 243 954 Effluent to MEE Zinc Chloride 34 Formation Step 2 Water 718
NMP 489 852 Effluent to Incinerator TMC 259 Formation Step 3 474 NMP Recovery Sodium Methoxide 80
Toluene 786 761 Recoverd Toluene NaH in Paraffin 48 413 Effluent to ETP Formation Step 4 Isobutyryl chloride 133 1000 PFD DM Water 572
Total 5225 5225
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74. 4-Chloro-N-[[4-(1, 1-Dimethylethyl) Phenyl] Methyl]-3-Ethyl-1- Methyl-1H-Pyrazole-5-Carboxamide Manufacturing Process: 4-chloro-3-ethyl-1-mehtyl-1H-pyrazole-5-carbonyl chloride is agitated with 1- (4-tertbutylphenyl) methanamine and NaOH which gives product TBNF. Chemical Reaction:
CH3 H C CH O H3C Cl 3 3 Cl NaOH NH NaCl CH H2O N O N 3 + H3C N + + N CH3 CH3 H3C H3C Cl NH2 N-(4-tert-butylbenzyl)-4-chloro-3-ethyl-1- 4-chloro-3-ethyl-1-methyl-1H- 1-(4-tert-butylphenyl)methanamine methyl-1H-pyrazole-5-carboxamide pyrazole-5-carbonyl chloride
Mass Balance: Mass balance of TBFN (4-chloro-N-[[4-(1,1-dimethylethyl)phenyl]methyl]-3-ethyl-1- methyl-1H-pyrazole-5-carboxamide) Kg Kg 4-chloro-3-ethyl-1- methyl-1H-pyrazole- 1081 674 Residue to Incinerator 5carbonyl Chloride 1-(4-tert- Formation of butylphenyl)methanami 597 intermediate-1 406 Effluent to MEE ne NaOH 81 505 Effluent to ETP Water 826 1000 TBFN
Total 2585 2585
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75. Tolfenpyrad Manufacturing Process: Step-1 Methylethyl Ketone reaction with diethyl ethanedioate, Sodium Ethoxide and HCl in Toluene forms intermediate DKE. Step-2 DKE is further treated with Hydrazine Hydrate in toluene forms EPE. Step-3 EPE along with dimethyl sulfate, Sodium hypochlorite, Sodium Hydroxide and Hydrochloric Acid forms EMCA. Step-4 4-methylphenol and 4-chlorobenzonytrile and sodium hydroxide with Dimethyl Formamide (DMF) forms TOBN. Step-5 Hydrogen gas is allowed to pass through mass of TOBN with solvent methanol. This reaction gives TOBA. Step-6 Reaction of EMCA (obtained in step-3), thionyl chloride, Sodium Hydroxide and TOBA in solvent Toluene forms final product TLF. Chemical Reaction: Step I
O CH3 CH O OC2H5 3 Solvent: Toluene H3C C H ONa 2 5 + HCl H C O + + 3 C H OH O + 2 5 + NaCl O OC2H5 O O
Methylethyl ketone diethyl ethanedioate ( DKE) M F = C H O 4 8 M F = C H O F W = 72.10 6 10 4 M F = C H O F W = 146.14 8 12 4 F W = 172.17 Step II
CH3
O CH3 O Solvent: TolueneN H3C O + NH2NH2 . H2O N + 3 H2O O O H O ( DKE) CH Molecular Formula = C H O hydrazine hydrate 3 8 12 4 ( EPE) Formula Weight = 172.17 Molecular Formula = H6N2O Formula Weight = 50.06 Molecular Formula = C8H12N2O2 Formula Weight = 168.19308 Step III
CH3
H3C
O N Solvent: water Cl N (CH ) SO NaOCl N Na SO H O NaCl 3 2 4 2 NaOH HCl CH3OH C2H5OH+ 2 4 + 2 + H O + + + + + + dimethyl sulfate N O H3C CH3 Molecular Formula = C2H6O4S Formula Weight = 126.13 HO ( EPE) (EMCA) Molecular Formula = C8H12N2O2 Formula Weight = 168.19 M F = C7H9ClN2O2 F W = 188.61
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Step IV
Cl CH3
H3C CN Solvent: DMF + NaOH + + NaCl + H2O O CN OH
4-methylphenol 4-chlorobenzonitrile (TOBN) Molecular Formula = C H O 7 8 Molecular Formula = C H ClN Molecular Formula = C H NO Formula Weight = 108.13 7 4 14 11 Formula Weight = 137.56 Formula Weight = 209.24
Step V
H3C CN H C Solvent: methanol 3 NH2 + 2 H2
O O
4-(4-methylphenoxy)benzonitrile (TOBN) Hydrogen Gas 1-[4-(4-methylphenoxy)phenyl]methanamine ( TOBA)
Molecular Formula = C14H15NO Molecular Formula = C14H11NO Molecular Formula = H2 Formula Weight = 209.24 Formula Weight = 2.01588 Formula Weight = 213.275
Step VI
Cl H3C H3C OH NH2 N + SOCl2 + 2NaOH + N O O thionyl dichloride CH3
Molecular Formula = Cl2OS TOBA EMCA Formula Weight = 118.97
Molecular Formula = C7H9ClN2O2 Formula Weight = 188.61
Solvent: Toluene
H3C Cl O
SO2 2 NaCl 2 H O N + + + 2 NH N CH3
H3C O TLF
Molecular Formula = C21H22ClN3O2 Formula Weight = 383.87
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Mass Balance: Mass balance of TLF(Tolfenpyrad) Kg Kg Stage-I Methyl Ethyl Ketone 246 201 Salt to incineration 489 Effluentto MEE Diethyl Ethanedioate 92 Formation of DKE Sodium Ethoxide 287 199 Toluene recovered HCl 19 236 Mek recovered Toluene 208
Hydrazine Hydrate 350 677 Effluent to ETP Water 361 Formation of EPE 585 Toluene recovered Toluene 609
DMS 424 771 Effluent to MEE Sodium Oxychloride 330 464 Salt to incineration Sodium Hydroxide 122 Formation of EMCA 370 Effluent to Incinerator HCl 21 943 EMCA Water 823
Stage-II 4-methyl Phenol 462 165 Residue to Incinerator 4-chloro benzonitrile 850 63 Effluent to ETP Formation of TOBN NaOH 97 1161 DMF recovered DMF 1222
Hydrogen 31 235 Effluent to ETP Methanol 1106 Formation of TOBA 1083 Methanol Recovered 810 TOBA
EMCA (Stage-I) 943 339 Salt to Incineration TOBA (Stage-II) 810 212 SO2 Scrubbed Thionyl Chloride 156 Formation of TLF 788 Effluent to ETP DM Water 371 1000 TLF NaOH 58
Total 10395 10395
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76. 3-Isobutyl Aniline Manufacturing Process: Step-1 MBC and IBC reacted with each other in an agitation reaction with addition of aluminum chloride and water forms CIBP.
Step-2 Nitration of CIBP with HNO3 forms CNIBP. Step-3 Dechlorination of CNIBP with addition of potassium carbonate with Hydrogen gas forms AIBP. Step-4 AIBP is treated with hydrazine and potassium hydroxide forms IBA.
Chemical Reaction: Step I
AlCl 3 H3C CH3 H3C CH3 + + 4 Al( OH ) O + 3 Cl 3 H Cl O 2 Cl Chlorobenzene Isobutyroyl chloride 1-(4-chlorophenyl)-2-methylpropan-1-one
MCB IBC CIBP
Step II
H3C CH3 H3C CH3 HNO 3 O O2N O + H2O.
Cl Cl 1-(4-chlorophenyl)-2-methylpropan-1-one 1-(4-chloro-3-nitrophenyl)-2-methylpropan-1-one
CIBP CNIBP
Step III
H C CH H3C CH3 H3C CH3 H3C CH3 3 3 4 H H N O N H2N 2 2 H2N OH O O O + + + KCl + KHCO3 + Cl Cl K2CO3, 2 H2 HIBA CNIBP AIBP CAIBP
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Step IV
H3C CH3 H3C CH3 NH2-NH2.H2O H2N O H2N
KOH / DEG + N2 + 3 H2
1-(3-aminophenyl)-2-methylpropan-1-one 3-Isobutylaniline
AIBP IBA Mass Balance: Mass balance of IBA Kg Kg MCB 695 445 HCl By-product Aluminium Chloride 539 84 Effluent to MEE Formation of Step 1 IBC 475 DM Water 973
Fuming Nitric Acid 652 80 Effluent to MEE DM Water 236 Formation of Step 2
Potassium Carbonate 8 115 Wet Cake to Incinerator DM Water 135 Formation of Step 3 Hydrogen gas 26
Diethylene Gylcol 486 177 Residue to Incinerator Potassium Hydroxide 125 477 DEG recocvered Hydrazine Hydrate 182 Formation of Step 4 1302 Effluent to MEE Water 293 1144 Effluentto ETP 1000 IBA
Total 4824 4824
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77. 3-[[[5-(Difluoromethoxy)-1-Methyl-3-(Trifluoromethyl)-1H- Pyrazol-4-yl] Methyl] Sulfonyl]-4, 5-Dihydro-5,5-Dimethyl Isoxazole Manufacturing Process: Step-1 Glyoxalic Acid with Hydroxy amine sulphate forms an intermediate which on further addition of bromine and sodium carbonate forms n-butyl acetate solution. Step-2 Then thiourea is added to this solution in HCl gives ITCA solution. Step-3 MTP with formaldehyde and sodium hydroxide gives HTMP which on further addition of potassium carbonate in acetonitrile gives FMTP in acetonitrile solution. Step-4 FMTP dissolved in acetonitrile and thionyl chloride forms CMTP. ITCA and Sodium hydroxide reaction forms SIO in solvent Butyl Acetate. CMTP and SIO forms ISFP with solvent Acetonitrile. Step-5 ISFP oxidized with Hydrogen peroxide in solvent acetonitrile forms the final product Octopussy.
Chemical Reaction: Step I
OH OH
H O N N CHO 2 Br2 (HONH ) H SO + 2 2 2 4 + CO2 HOOC Na CO COOH Step-A :BX 2 3 Br Br H O Glyoxalic acid Hydroxy amine sulphate 2 BX HIA n-Butyl acetate solution
H3C CH3 Step-B :BIO CH 2
Na2CO3
O N CH3 NaBr + CH3 Br BIO n-Butyl acetate solution
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Step II
O S N CH 3 NH 2 O HCl N + C H C H 3 3 HBr Br H N N H HN S + 2 2 C H3 BIO n-Butyl acetate solution Thiourea ITCA aq. Solution
Step III
F3C F3C OH F3C OH
HCHO CHF Cl / K CO N 2 2 3 OH N N N ONa OCHF NaOH N N 2 Acetonitrile CH 3 CH3 CH3
MTP HMTP FMTP Aq. solution Acetonitrile solution
Step IV
F3C OH F3C Cl
N SOCl OCHF 2 N HCl SO N 2 OCHF 2 N 2 + + CH 3 CH3
FMTP CMTP Acetonitrile solution O CH3 N CH3
S F3 C N O NH2 N O HBr CH3 N CH OCHF 2 3 N HN NaS CH3 S C H NaOH 3 CH3
ITCA SIO ISFP aq. solution aq. solution Acetonitrile solution
Step V
CH3 CH O O 3 N CH3 N CH3 O F3C S F3C S O 2H O 2H O + 2 2 N + 2 N N OCHF2 N OCHF2 Acetonitrilre CH3 CH3 ISFP Octopussy
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Mass Balance: Mass balance of Octopussy Kg Kg Stage-I Hydroxyl amine sulfate 250 23 CO2 to caustic scrubber DM Water 418 598 NaBr By-product Glyoxalic acid 753 Formation of BX NaOH 174 Na2CO3 13 Bromine 1007
Sodium carbonate 69 89 Effluent to ETP Formation of BIO Butyl acetate 1141 303 NaBr By-product
Thiourea 270 727 HBr by-product HCl soln. 45 Formation of ITCA 1947 ITCA Water 642 1096 n-Butyl Acetate Stage-II NaOH 38 963 Acetonitrile recovered MTP 389 173 Effluent to ETP farmaldehyde 142 983 FMTP Acetonitrile 983 Formation of FMTP K2CO3 31 Difluorochloromethane 263 Water 272
NaOH solution 811 997 Effluent to MEE Caustic Scrubber
67 HCl + 118 SO2 FMTP (Stage-II) 983 ITCA (Stage-I) 1947 1275 Effluent to ETP Formation of ISFP Thionyl chloride 254 NaOH. 74
H2O2 68 298 Effluent to ETP Water 594 177 Residue to Incinerator ACN 262 Formation of Octopussy 254 Recycled ACN 993 Effluent to MEE 1000 Octopussy Total 11895 11896
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78. 3-[1-(3, 5-Dichlorophenyl)-1-Methylethyl]-3,4-Dihydro-6-Methyl-5- Phenyl-2H-1,3-Oxazin-4-one Manufacturing Process: Step-1 DCT reacts with acetyl chloride & aluminum chloride and forms DCMACP. Step-2 DCMACP is then treated with sodium hypochlorite and HCl forms DCMBA. Step-3 Then thionyl chloride is added to DCMBA, which forms DCMBC. Step-4 Further DCMBC and 1, 3 Dimethyl 5-pyrazolone is treated with TEA forms MY-71-OH. Step-5 DCMHP treated with 2-Chloro-1-(4-methyl phenyl) ethanone along with
K2CO3 forms final product MY-71. Chemical Reaction: Step I
CH3 CH3 Cl Cl Cl Cl O AlCl 3 H O + HCl + Al(OH)3 + + 3 + 2 O H3C Cl
CH 2,6-dichlorotoluene acetyl chloride 3 (DCT) 1-(2,4-dichloro-3-methylphenyl) ethanone (DCMACP)
Step II
CH3 CH3 Cl Cl Cl Cl 2 NaOH + CHCl3 + + NaCl 3 NaOCl + + HCl O O
OH CH3 2,4-dichloro-3-methylbenzoic 1-(2,4-dichloro-3-methyl acid(DCMBA) phenyl)ethanone
Step III
CH3 CH3 Cl Cl Cl Cl SO HCl + 2 + + SOCl2 O O
Cl OH 2,4-dichloro-3-methylbenzoyl 2,4-dichloro-3-methylbenzoic chloride(DCMBC) acid(DCMBA)
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Step IV
O Cl H3C CH3 H3C Cl Cl TEA CH3
+ N N + TEA. HCl O N O N OH Cl Cl H3C H3C 2,4-dichloro-3-methylbenzoyl (2,4-dichloro-3-methylphenyl)(5-hydroxy-1,3-dimethyl- chloride (DCMBC) 1,3-dimethyl -5-pyrazolone 1H-pyrazol-4-yl)methanone (MY-71-OH)
Step V
O Cl O Cl CH H3C H3C 3 CH3 CH3 N N K CO + + 2 3 + KCl + KHCO N 3 N Cl Cl O OH Cl CH O H3C 3 H3C (2,4-dichloro-3-methylphenyl) 2-Chloro-1-(4-methyl (5-hydroxy-1,3-dimethyl-1H- phenyl)ethanone pyrazol-4-yl)methanone O (DCMHP) MY-71
Mass Balance: Mass balance of MY 71 Kg Kg AlCl3 901 2,6- Dichloro Toluene 496 239 HCl By-product Formation of Step 1 Acetyl Chloride 940 676 Al(OH)3 Recovered Water 817
Sodium Hypochlorite 99 Formation of 420 Salt to Solid Incinerator Hydrochloric Acid 45 intermediate-2 96 Effluent to ETP
SO2 + HCl scrubber SOCl2 276 Formation of 100 spent intermediate-3 Caustic 362 200 Effluent to ETP
1,3-dimethyl-5- 296 1356 Effluent to MEE pyrazolone Formation of Triethyl Amine 193 intermediate-4 Water 477
Potassium carbonate 98 913 Effluent to Incinerator Formation of MY 71, 1000 MY71
Total 5000 5000
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79. 1-Methyl-3-(Trifluromethyl) 1H-Pyrazol-5-ol Manufacturing Process: Step-1 Ethyl trifluoro acetate and Ethyl acetate forms ETFAA in reaction with HCl Gas and Sodium ethanoate. Step-2 ETFAA treated with Methylhydrazin and acetic acid to form MTP. Chemical Reaction:
Step I
O O O O
NaOEt 2 C H OH F3C O CH3 2 5 + NaCl F3C O CH3 + H3C O CH3 + ethyl trifluoroacetate ethyl ethyl 4,4,4-trifluoro-3-oxobutanoate acetate Hydrochloric acid gas ETFAA ETFA
Step II NH O O F C H3C NH2 3 H O C2H5OH + 2 F3C O CH3 N + O OH N ethyl 4,4,4-trifluoro-3-oxobutanoate CH3 ETFAA H3C OH 1-methyl-3-(trifluoromethyl)-1H-pyra zol-5-ol MTP Mass Balance: Mass balance of MTP Kg Kg Recovered Ethyl Ethyl Acetate 1920 1730 Acetate ETFA 618 Formation of MTP 160 Recovered ETFA Sodium Ethoxide 313 737 Effluent to MEE HCl 348 17 Salt to Incinerator
Recovered MMH Acetic Acid 521 612 recycle Monomethyl Recovered ETFA 541 Formation of MTP 487 Hydrazine recycle Water 688 206 Effluent to ETP 1000 MTP
Total 4949 4949
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80. 1, 3-Dimethyl-5-Chloro-4-Pyrazolyl Carboxylic Acid Chloride Manufacturing Process:
Step-1 DMPO is reacted with POCl3 and DMF in water and agitation gives CDPC.
Step-2 CDPC is further oxidized with H2O2 along with NaOH and HCl, which at the end forms CDPA. Step–3 CDPA in a solution of DMF and Toluene reacts with thionyl chloride and forms final product DCPA. Chemical Reaction: Step I O
H3C H3C H H3C N N Cl NH.HCl + H PO N O + POCl3 + DMF N + 3 4 H O 2 H C CH3 CH3 3
DMPO CDPC Dimethylamine hydrochloride
Step II
H3C CHO H C 3 COOH
H2O2 + NaOH HCl NaCl 2 H O N + + N + + 2 N Cl N Cl
CH CH 3 3 CDPC CDPA
Step III
H3C COOH H C COCl 3 DMF N N + SO + HCl Cl + SOCl2 Cl 2 N Toluene N
CH3 CH 3 CDPA DCPA
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Mass Balance: Mass balance of DCPA Kg Kg DPMO 384 220 Effluent to ETP DMF 985 935 DM.HCl Recocvered POCl3 626 Formation of Step 1 Water 1278 NaOH 164
NaOH 135 1809 Effluent to MEE Hydrogen Peroxide 313 Formation of Step 2 HCl 65
Caustic Solution 481 488 Scrubber spent to MEE
6.83 SO2+ HCl Recovered Toluene- Toluene 998 979 recycled Formation of Step 3 DMF 6 465 Residue to incinerator SOCl2 461 1000 DCPA
Total 5896 5896
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81. 3, 4-Dichloro-5-Fluoro Biphenyl-2-Amine Manufacturing Process: Step-1 Magnesium turning, Tetrahydrofuran (THF), Grignard, and BDB solution in THF are agitated in a reactor which forms a mass. TMB solution in THF is reacted with this mass and agitated with Sulphuric Acid, Water and Sodium Chloride forming Boronic Acid suspension in water. Step-2 Above intermediate is treated with 2-Bromo-4-fluoroaniline; this mixture is agitated and addition of K3PO4 in toluene produce final product CFPA. Chemical Reaction: Step I HO OH Br B
OH THF + Mg + TBM + Mg + 3CH3OH Toluene, Br Cl Cl H2SO4, 3H2O Cl Cl
4-bromo-1,2-dichlorobenzene BDB-Boronic acid
Step II F HO OH B NH2 F
KBr B(OH) K2HPO 4 + + K3PO4 + + 3 + Cl NH2 Toluene, water Cl Br Cl Cl BDB-Boronic acid 2-bromo-4-fluoroaniline 3',4'-dichloro-5-fluoro biphenyl-2-amine Mass Balance: Mass balance of CFPA (3,4-dichloro-5-fluorobiphenyl-2-amine) Kg Kg Magnesium turnings 16 605 Effluent to MEE THF 1134 258 Residue to incinerator BDB 688 245 Toluene Recovered Formation of BDB TMB 671 1065 THF recovered Boronic Acid Sulphuric Acid 140 Toluene 266 Water 622
2-bromo-4- 556 392 Effluent to incinerator fluoroaniline K3PO4 30 Preparation of CFPA 1028 Effluent to ETP Toluene 243 220 Toluene recycled Water 447 1000 CFPA
Total 4813 4813
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82. 3-(Difluoro Methyl)-1-Methyl-1H-Pyrazole-4-Carboxylic Acid Manufacturing Process: Step-1 Ethyl 4, 4-difluro 3-Oxo butanoate, trimethyl orthoformate and acetic anhydride are agitated in reactor and forming Ethyl 4, 4 difluro -2- (methoxymethylidene)-3-oxobutenoate mixture. Step-2 Ethyl 4, 4 difluro -2-(methoxymethylidene)-3-oxobutenoate mixture is again mixed with Mono methyl hydrazine in presence of acetone and HCl forms a Mass. NaOH and H2SO4 is added in to that mass and after reaction further
SOCl2 is added and agitated producing the final product ACH. Chemical Reaction: Step I O CHF OC H CHF 2 OC2H5 2 2 5 H3CO H3C H 2 +H3CO + O + 2 CH3COOH + 2 CH3COOMe O O O O H3CO H3C Acetic acid Methyl acetate ethyl 4,4-difluoro-3- Trimethyl O OCH oxobutanoate orthoformate 3 Acetic ethyl 4,4-difluoro-2- anhydride (methoxymethylidene) -3-oxobutanoate
Step II
O O O O F F COOC H COOH NH F 2 5 F OEt Acetone H3C OEt NH2 F 47%NaOH F Na2SO4 + F + NaCl F 30% HCl N + + MeO N N EtO 40% H2SO4 N
CH3 CH3 MMH (Mixt. of O-Me/Et acrylate) PRZ-ester PRZ
SOCl2
O Cl F
HCl SO2 + + F
N N
CH3
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Mass Balance:
Mass balance of ACH (3-(difluoro methyl)-1-methyl-1H-pyrazole-4-carboxylic acid)
Kg Kg Ethyl 4,4-difluoro-3- 374 438 Acetic Acid recycle oxobutanoate Formation of Trimethyl Orthoformate 690 783 Effluent to ETP intermediate-1 Acetic Anhydride 551 Water 867
O-Ethyl Acrylate 424 716 Effluent to MEE Mono Methyl Hydrazine 466 734 Salt to Incinerator Acetone 406 398 Acetone recovery HCl 37 146 Effluent to ETP Formation of ACH SO2 + HCl Scrubber NaOH 94 104 spent to MEE H2SO4 134 1000 ACH SOCl2 275
Total 4319 4319
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83. 4-Bromo- 1, 2-Dichloro Benzene Manufacturing Process: Aluminum Chloride, dichlorobenzene, and Bromine are charged in a reactor and agitated forming final product BDB. Chemical Reaction:
Cl Cl
Cl Cl AlCl3 + Br Br + HBr
bromine hydrogen bromide 1,2-dichlorobenzene Br 4-bromo-1,2-dichlorobenzene Mass Balance: Mass balance of BDB Kg Kg ODCB 251 330 Effluent to MEE AlCl3 18 232 Residue to incinerator Bromine 1018 209 Effluent to ETP Formation of BDB HCl 44 1000 BDB Water 351 Na2S2O3 88
Total 1771 1771
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84. Difluoro Methyl-N-Methyl Pyrazolic acid Manufacturing Process: Step-1 Ethyl 4, 4-difluro-3-oxobutanoate and Trimethyloethoformate along with Acetic anhydride forms Oxobutanol derivative intermediate Step-2 MMH with mixture of O-Me/Et acrylate treated with acetone and HCl
form PRZ Ester which is further forms PRZ after addition of NaOH and H2SO4. Chemical Reaction: Step I O CHF OC H CHF 2 OC2H5 2 2 5 H3CO H3C H 2 +H3CO + O + 2 CH3COOH + 2 CH3COOMe O O O O H3CO H3C Acetic acid Methyl acetate ethyl 4,4-difluoro-3- Trimethyl O OCH oxobutanoate orthoformate 3 Acetic ethyl 4,4-difluoro-2- anhydride (methoxymethylidene) -3-oxobutanoate
Step II
O O O O F F COOC H COOH NH F 2 5 F OEt Acetone H3C OEt NH2 F 47%NaOH F Na2SO4 + F + NaCl F 30% HCl N + + MeO N N EtO 40% H2SO4 N
CH3 CH3 MMH (Mixt. of O-Me/Et acrylate) PRZ-ester PRZ
Mass Balance: Mass balance of PRZ (Difluoro Methyl-N-Methyl Pyrazolic acid) Kg Kg Ethyl 4,4-difluoro-3- 371 454 Rec. distillate to MEE oxobutanoate Formation of Recovered Acetic Acid Acetic anhydride 816 500 intermediate-1 as By-product Trimethylorthoformat 448 e
Acetone 449 777 Effluent to ETP MMH 475 Formation of 440 Acetone Recover Water 467 intermediate-2 Aq. HCl 71
NaOH 72 529 Effluent to ETP Water 495 Formation of PRZ 1000 PRZ H2SO4 37
Total 3700 3700
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Fluorospeciality Products 85. 2, 2-Difluoro Ethyl Amine Manufacturing Process: 2, 2-Difluoro -1-chlorethane and Ammonia react with each other in auto clave to form 2, 2-difloroethyl amine
Chemical Reaction:
Autoclave F H2N Cl 2 NH (gas) F NH Cl 3 + 4 + F F NMP Ammonium chloride 2,2-Difluoro-1-chlorethane Ammonia 2,2-Difluoroethyl amine Mass Balance: Mass balance of DFEA Kg Kg NMP 2272 2204 NMP Recovered Ammonia 520 417 Effluent to MEE DFCE 395 Formation of Step 1 333 Effluent to ETP Water 815 48 Residue to Incinerator 1000 DFEA
Total 4002 4002
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Pharma Intermediates 86. Ethyl-4-Methyl-1, 3-Thiazole-5-Carboxylate Manufacturing Process: Step-1 Ethyl acetoacetate and Sulfuryl Chloride reacts and forms Ethyl -2- chloroacetoacetate Step-2 Formamide and Phosphorus pentasulfide treated with each other and THF to form Thioformamide. Step-3 Ethyl -2-chloroacetoacetate and Thioformamide aging treated with THF to form final product EMTC Chemical Reaction: Step I
O O O O SO Cl SO HCl + 2 2 OEt + 2 + OEt Cl Ethyl acetoaetate Sulfuryl chloride Ethyl-2-chloroacetoacetate
Step II
O THF S 5 + P2S5 5 + P2O5 H NH2 H NH2
Formamide Phosphorus pentasulfide Thioformamide
Step III
O O S THF N OEt OEt + HCl H2O H NH2 S + + Cl O Ethyl-2-chloroacetoacetate Thioformamide EMTC
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Mass Balance:
Mass balance of EMTC Kg Kg Stage-I Ethyl acetoacetate 1433 701 SO2 to scrubber Sulfuryl Chloride 1478 Formation of Step-1 400 HCl By-Product 1811 Conc. Mass ECAA
Stage-II Phosphorous Pentoxide THF 1138 632 to Incinerator Formation of Step-2 Formamide 707 1115 Recovered THF Phosphorous 859 958 Thioformamide Pentasulphide
Conc. Mass ECAA (Stage- 1811 888 Effluent to MEE I) THF 1138 1115 THF Recovered 958 Formation of EMTC 743 HCl By-product Thioformamide (Stage-II) DM Water 746 340 Residue to Incinerator 566 Effluent to ETP 1000 EMTC
Total 10268 10268
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Speciality Chemicals 87. Methyl cis-1-[2-(2, 5-Dimethylphenyl)-Acetylamino]-4-Methoxy- Cyclohexane Carboxylate Manufacturing Process: Step-1 Ammonia gas and Carbon dioxide gas dissolved in water forms Ammonium Carbonate in equilibrium with ammonium carbamate.
Step-2 4-methoxy cyclohexanone treated with NaCN and (NH4)2CO3 in solution of Water forms Isomers of Hydantoin which is further treated with NaOH for cis- Isomer of Hydantoi-Na Step-3 Cis-Isomer of Hydantoi-Na treated with KOH and Water forms Amino Acid salt. Step-4 Amino Acid is treated with (2, 5-dimethyl phenyl) acetyl chloride, KOH and HCl, forms Acid Amide
Step-5 Acid amide reaction with methanol, H2SO4 and Chlorobenzene forms Ester Amide. Chemical Reaction: Step I
2 NH CO H O (NH ) CO H O + 2 + 2 4 2 3 H2NCOONH4 + 2 Ammonia Ammonium carbonate Ammonium carbamate (FW:17.03) (FW:44.01) (FW:96.08) (FW:78.07)
Step II O O O NH NaOH N Na + NaCN + (NH4)2CO3 O O H O N 2 O N O O H H
4-Methoxycyclohexanone cis/trans - Hydantoin cis - Hydantoin -Na
(FW:128.17) (FW: 49.01) (FW:96.08) (FW:198.22) (FW:220.2)
NaOH H O + NH4OH + + 2 (35.05) (40) (18.02)
Step III O O N Na H O K CO O + 2 KOH + 2 O ONa + 2 3 + NH3 N O NH H 2
cis - Hydantoin -Na Amino Acid (salt)
(FW:220.2) (FW:56.12) (FW:18.01) (FW:195.2) (FW:138.21) (FW:17.03)
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Step IV O O Cl i) KOH O O ONa KCl NaCl H O + O + + + 2 ii) HCl NH NH2 O OH
Amino Acid (salt) (2,5-dimethylphenyl)acetyl chloride Acid amide
(FW:195.2) (FW:182.65) (FW:319.4)
Step V
O O
O H2SO4 O + CH3OH H O NH chlorobenzene NH + 2 HO O O O
Acid amide Ester amide (FW:319.4) (FW:32.04) (FW:333.42)
Mass Balance: Mass balance of ETMD Kg Kg Ammonia 901 614 Effluent to ETP Carbon Dioxide 67 Formation of Step 1 Water 345
Sodium cyanide 162 964 Effluent to ETP 4-methoxy- 385 cyclohexanone Formation of Step 2 NaOH 96 Water 605
KOH 71 760 Effluent to MEE Formation of Step 3 DM Water 545
KOH 92 452 Effluent to MEE DM Water 20 2,5-Dimethylphenyl Formation of Step 4 394 acetyl chloride HCl 22
MCB 1700 163 Effluent to MEE Distilled MCB Methanol 173 Formation of Step 5 1659 recovered Sulphuric Acid 35 1000 ETMD
Total 5612 5612
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88. 1, 1, 1, 3, 3, 3-Hexafluoro Isopropyl Methyl Ether Manufacturing Process: Step-1 OIME and KOH along with TMAC form intermediate HIME.
Step-2 HIME, sodium hypochlorite, NaHCO3, and H2O forms MTTHP. Step-3 MTTHP reacts with dimethyl sulphate along with NaOH and forms MTTMP. Step-4 NaOH is gradually added to the above reaction mass and agitation of the same produce TTMP. Step-5 After giving appropriate settling to the above intermediates provides two isomers of the same and forms HFMOP isomer along with another isomer Olefine.
Step-6 Both isomers are then treated with KF and H2O in addition of DMF forms HFMOP. Chemical Reaction: Step I CF 3 CF F 3 TMAC F C CH KOH O 3 3 + F C CH O 3 3 KF H2O F + + F
OIME HIME
Step II
CF3 COOCH O F C 3 H O 3 H O F3C CH3 12%NaClO NaHCO3 2 NaF CO 2 + + + OH + NaCl + + 2 + F F3C HIME MTTHP
Step III
COOCH3 COOCH F3C F C 3 CH NaSO H O 3 Me SO + NaOH 3 4+ 2 2 4 O CH3 + OH + F3C F3C MTTHP MTTMP
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Step IV COOCH COONa F C 3 3 F3C CH OH O O 3 F C 48%NaOH + 3 + F3C CH 3 CH3 MTTMP TTMP
Step V
CF3 NaHCO CH3 + 3 COONa F3C O F3C DMF O H2O HFMOP F3C + CH3
TTMP H3C CF3 O CO +NaF+ 2 + H2O F F Olefine
HFMOP+Olefine in DMF Solution
Step VI
CF3
CH3 F3C O
HFMOP CF3 CH KF H O 3 KOH + + 2 F3C O + H C + CF 3 3 HFMOP O F F Olefine
HFMOP+Olefine in DMF Solution
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Mass Balance:
Mass balance of HFMOP Kg Kg Water 298 745 Effluent to MEE OIME 1983 Formation of Step 1 TMAC 31 KOH 76
Sodium Bicarbonate 44 155 Salt to incinerator Formation of Step 2 Sodium Hypochlorite 60
Dimethyl sulfate 927 102 Effluent to MEE Formation of Step 3 Sodium Hydroxide 255
Sodium Hydroxide 170 1404 Methanol_Recover Formation of Step 4 Water 420 59 Residue to Incineration
Water 75 737 Effluent to ETP Formation of Step 5 DMF 715
Water 122 225 Effluent to ETP KF 133 202 Residue to incinerator Formation of Step 6 680 DMF Recovered 1000 HFMOP
Total 5309 5309
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89. 2, 2-Dimethyl-4-Methylene-1, 3-Dioxalane Manufacturing Process: Step-1 Acetone and Epichlorohydrin is treated with TBA forms CMDD. Step-2 CMDD on further reaction with KOH forms MDO. Chemical Reaction:
Step I O O H3C CH3
Tributylamine H C CH O O 3 3 +
Cl Cl
Acetone Epichlorohydrin 4-(Chloromethyl)-2,2-dimethyl-1,3-dioxalane ECH CMDD
Step II
H3C CH3 H3C CH3
O O O O KCl H O + K OH + + 2
Cl CH2 4-(Chloromethyl)-2,2 Potassium Hydroxide 2,2-dimethyl-4-methylene- -dimethyl-1,3-dioxalane 1,3-dioxalane CMDD (KOH) MDO
Mass Balance: Mass balance of MDO Kg Kg Distilled Acetone- Acetone 981 687 recycled Formation of Step 1 Epichlorohydrin 1100 364 Effluent to ETP Tributyl amine 13
Tetra Ethylene Glycol 472 526 Effluent to MEE Filtered solid to KOH 51 Formation of Step 2 97 Incinerator DM Water 519 462 TEG recovered 1000 MDO
Total 3136 3136
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90. Chloro Methyl 2-Methyl Propanoate Manufacturing Process: Isobutyryl chlorine and Paraformaldehyde react with each other in an agitator and form Chloromethyl 2-Methyl Proponoate. Chemical Reaction:
O O
Cl CH3 (HCHO) Cl O H3C + n CH3 CH3
Isobutyryl chloride Paraformaldehyde chloromethyl 2-methylpropanoate
Mass Balance: Mass balance of CMIBA Kg Kg Wet Cake to Isobutyryl Chloride 918 17 incinerator Formation of Residue to liquid Paraformaldehyde 260 177 CMIBA incinerator Anhydrous Zinc 17 1000 CMIBA Chloride
Total 1195 1195
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91. 2-Chloro-4-(Methyl sulfonyl)-3-[(2, 2, 2-Trifluoroethoxy) Methyl] Benzoic Acid Manufacturing Process: AE-014 and TFE are treated with NaOH prills and acetonitrile along with Dichloro benzene to forms CMTB. Chemical Reaction:
OH Cl OH Cl F F + O O H O Br Na F + NaBr + 2 O HO O F + F S F S O DMF/Toluene O H3C H3C
2-chloro-4-(methylsulfonyl)-3-[(2,2, TFE AE-014 2-trifluoroethoxy) methyl] benzoic acid
Mass Balance: Mass balance of CMTB (2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluoroethoxy) methyl] benzoic acid) Kg Kg AE-014 438 20 H2 to atmosphere DMF 1463 556 Effluent to MEE NaH 175 422 Effluent to ETP Tri Fluoroethanol 878 Formation of CMTB 2042 Toluene recovered Toluene 2083 200 Residue to Incinerator NaOH 68 1404 DMF recycled Water 540 1000 CMTB
Total 5644 5644
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Performance Chemicals 92. 1-(4-Chlorophenyl)-2-Methyl-2-(Morpholin-4-yl) Propan-1-one Manufacturing Process: Step-1 Acylation of Chlorobenzene and 2-methyl propanoyl chloride in addition of Aluminum Chloride forms CIBP Step-2 Bromination of CIBP along with EDC forms BCIBP. Step-3 BCIBP treated with sodium methanoate forms CIBO. Step-4 A coupling reaction of CIBO with morpholine forms final product PCBM.
Chemical Reaction: Step I
H3C CH H3C Cl AlCl 3 Cl Cl + + 4 + Al(OH)3 H3C O O chlorobenzene 2-methylpropanoyl chloride 1-(4-chlorophenyl)-2-methylpropan-1-one
(CIBP) Step II
H C Br 3 H3C CH3 EDC CH3 HBr Cl + Br Cl + O O 2-bromo-1-(4-chlorophenyl)-2-methylpropan-1-one 1-(4-chlorophenyl)-2-methylpropan-1-one (BCIBP) Step III Br H C CH H3C 3 3 NaOMe CH Cl 3 Cl O + NaBr O OMe 2-bromo-1-(4-chlorophenyl)-2-methylpropan-1-one 2-(4-chlorophenyl)-2-methoxy-3,3-dimethyloxirane (CIBO) Step IV O H H3C CH3 N Cl CH3 MeOH Cl O + N + H C OMe O 3 O
2-(4-chlorophenyl)-2-methoxy- morpholine 1-(4-chlorophenyl)-2-methyl-2- 3,3-dimethyloxirane (morpholin-4-yl)propan-1-one (PCBM)
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Mass Balance: Mass balance of PCBM Kg Kg MCB 1991 1286 HCl by-product Aluminum Chloride 1770 392 Effluent to ETP Formation of Step 1 Isobutyryl Chloride 1247 1416 Al(OH)3 Water 208
1,2-Dichloro Ethane 428 837 HBr By-product Bromine 1204 924 Effluent to ETP Formation of Step 2 1,2-Dichloro Ethane- NaHCO3 76 698 recycled Water 1539
Sodium Methoxide 1178 1032 NaBr By-product Formation of Step 3
Morpholine 623 543 Methanol-recycled Formation of Step 4 2136 Effluent to MEE 1000 PCBM
Total 10264 10264
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93. Titanium Biscatecholate Monopyrogallate Sodium Potassium salt Manufacturing Process: Step-1 Mass of catechol and toluene treated with TiCl4 forms Intermediate mass Step-2 Further this Intermediate mass is treated with NaOH followed by KOH and EDTA-H forms Negolyte. Chemical Reaction: H O O 2- OH OH Ti Cl O OO HO OH OH OH Cl Ti Cl 4HCl + 2 + + Cl HO
Catechol Toluene Ticl4
H2TiCat2Py H O ONa O O 2- 2- Ti Ti O O O O O O OK OH + NaOH + KOH + EDTA -H + + 2H2O HO HO EDTA -Na -K
NaKTiCat2Py
H2TiCat2Py NEGOLYTE Mass Balance: Mass balance of Negolyte
Kg Kg Catechol 883 398 HCl by-product Toulene 1970 1880 Toluene recycled Ticl4 517 1438 Effluent to ETP NaoH 218 Formation of Negolyte 1000 Negolyte KOH 305 DM water 793 EDTA 28
Total 4716 4716
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Annexure-III Water Consumption Sr. Source Existing Total after No. (KLD) Expansion (KLD) I Domestic 30 60 II Gardening 40 148 III Industrial a) Process 305 253 b) Scrubber 60 125 c) DM Water treatment 00 177
d) Boiler 400 460 e) Cooling 1360 1480 f) Lab 00 20 g) Washing 00 250 Total Industrial 2125 2765 Total (I+II+III) 2195 2973 Recycle water -- 134 Actual fresh water -- 2839 requirement
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Wastewater Generation
Sr. Source Existing Total after No. (KLD) Expansion (KLD) I Domestic 30 50 II Gardening 00 00 III Industrial a) Process 610 522 b) Scrubber c) DM Water treatment 00 177 d) Boiler 70 70 e) Cooling 350 296 f) Lab 00 20 g) Washing 00 250 Total Industrial 1030 1335 Total (I+II+III) 1060* 1385**
* Total w/w generation is around 1060 KLD; out of which 60 KLD goes to incinerator and remaining 1000 KLD waste water generation goes to ETP.
** Total w/w generation will be tune around 1385 KLD after expansion. Out of which 60 KLD goes to incinerator, 19 KLD system losses & salt generation and 134 KLD treated water recycle and resulted 1172 KLD waste water generation goes to ETP.
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Water Balance Diagram-Existing
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Water Balance Diagram - Total after Expansion
Water consumption 2973 KLD (2839 Fresh + 134 recycle)
Domestic Process water Washing Lab Utilities Green belt 60 378 250 20 1983+134* 148
DM treatment 2117 Process Scrubber DM rejects 253 125 177 By- Treated water 209 60 Product 1940 from RM 65 Domestic effluent 50 Cooling Boiler 1480 460 ETP Incinerator 170 232 60 Bleed off Blow down 296 70
Salt MEE System Loss Filter 9.0 292 10 296+70+177=543
To TSDF Blow 273 down 343 ETP RO RO Permeate 50+170+273+250+20+ 134*
66+343=1172 RO Reject 66
Finally discharged into SEZ common sump
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Annexure IV Effluent Treatment Plant - Existing
CAPACITY & FLOW DIAGRAM OF EFFLUENT TREATMENT PLANT Capacity: 2500 M3/Day Parameter Characteristics Effluent Raw Effluent pH 2 to 10 COD 8000 mg/l Oil & Grease Trap TDS 4000 mg/l Capcity: 30 M3 BOD 5000 mg/l
Equalization Tank Capacity:1500 M3
Flash Mixer Tank Capacity: 60 M3
After Primary pH 7.5 to 8.0 Clariffocculator Tank Treatment Capacity: 187 M3 COD <6000 mg/l BOD <3750 mg/l O & G <10 mg/l TSS <100 mg/l AT - 1 Capacity: 3000 M3
After Clarifier- 1 pH 7.5 to 8.0 Clariffer -1 COD <900 mg/l Capacity: 187 M3 BOD <562 mg/l O & G <10 mg/l TSS <100 mg/l AT - 2 Capacity: 1500 M3
Clariffer -2 After Clarifier- 2 pH 7.5 to 8.0 Capacity: 187 M3 COD <270 mg/l BOD <168 mg/l Sludge Holding O & G <10 mg/l TSS <100 mg/l Sand Filter
Sludge Dewatering
Activated Carbon Dewatered Sludge Filter to SLF
Final Outlet pH 7.0 to 8.5 meeting the COD <250 mg/l SPCB norms BOD <100 mg/l Guard Pound O & G <10 mg/l Capacity: 4500 M3 TDS <5000 mg/l TSS <100 mg/l Treated Effluent Discharge to Sea through ECPL's effluent disposal system We will use the same ETP after Expansion.
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MEE Flow Diagram
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Annexure-V Details of Hazardous/Solid waste
Sr. Type of Category of Existing Total Disposal facility No. Waste Waste as per Quantity after HWM Rules Expansion 2016 Quantity 1. ETP Sludge & 35.3 395.41 900 MTPM Collection, Storage, MTPM 2700 Transportation & Disposal in MEE salt 1216.67 MTPM approved common TSDF/co- MTPM processing. 2 Used Oil 5.1 15.16 25 Collection, storage and reused KL/month KL/month or sold to registered refiners 3 Residues after 20.3 243.33 20000 Collection, storage, & distillation, MTPM MTPM Incineration in house or in fractionation, approved common condensation incineration facility or co- recovery Processing / incineration etc./Solvent Distillation Residue 4 Spent Carbon 36.2 16.67 50 MTPM Collection, storage & MTPM Incineration in house or in approved common incineration facility or Send to Authorized recyclers/ re- processors for recovery/co- processing 5 Process Waste 29.1 60.76 1800 Collection, storage, & (Process Waste MTPM MTPM Incineration in house or in Sludge/residue) approved common incineration facility or Co- processing/co-incineration facility 6 Incineration 37.2 456.25 1000 Collection, Storage, Ash MTPM MTPM Transportation & Disposal in approved common TSDF site. 7 Discarded 33.1 30.41 300 MTPM Recycled or sold to authorized containers / MTPM & scrap dealer or end users or drums/ 50000 disposal in approved common liners NOSPM TSDF/incineration in-house as well approved common facility or sent for common decontamination facility 8 Date Expired 29.3 0.91 100 MTPM Collection, storage, & off specification MTPM Incineration in house or in products approved common incineration facility/co- processing 9 Spent/Crude 29.4 121.67 30000 Collection, storage, & Solvent MTPM MTPM Incineration in house or at authorized CHWI facility or Co-processing or reuse by in- house solvent distillation. In Some of the product where purity requirements are very high, recycling is not possible due to build-up of moisture or some specific impurity, such
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solvents are required to be sent to authorized as well as CPCB registered solvent distillation unit. Sold to GPCB Authorized recyclers/distillators/re- processor 10. Spent Catalyst 29.5 -- 50 MTPM Collection, storage & Incineration in house or in approved common incineration facility or co- processing, Send to Authorized recyclers/ re- processors for recovery or sent for regeneration to supplier. 11. Spent Acid 29.6 -- 1500 Collection, storage, & MTPM Incineration in house or in approved common incineration facility or co- processing, Send to Authorized recyclers/ re- processors, reuser 12. Spent Resin 34.2 0.125 2 MTPM Collection, storage, MTPM transportation and disposal in approved common TSDF 13. NaBr/MgBr -- 5000 Collection, storage, MTPM transportation and sold to bromine manufacture or any recovery or processing or incineration/co-processing/ common effluent treatment
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Annexure-VI Source of Air Emissions
Sr. Stack attached to Fuel Stack APC measures Probable No. Type Height emission in m Flue Gas Stacks-Existing 1 Boiler (03 Nos.) FO/NG 54 -- PM <150 mg/Nm3 2 Thermic Fluid Heater FO/NG 20 -- SO2 <100 ppm (01 Nos.) NOx <50 ppm Flue Gas Stacks-After Expansion 1 Boiler (03 Nos.) FO/NG 54 -- PM <150 mg/Nm3 2 Thermic Fluid Heater FO/NG 20 -- SO2 <100 ppm (01 Nos.) NOx <50 ppm 3 DG Set-06 Nos: 4000 HSD 11 -- KVA each Process Gas stacks- Existing
1 Process Stack MPP-5 -- 26.5 Alkali Scrubber HCl:<20 mg/Nm3 3 Cl2:<9 mg/Nm 3 NH3:<30 mg/Nm Pesticide compound in form of Particulate matter :<20 mg/Nm3 3 H2S:<45 mg/Nm 2 Process Stack MPP-6 -- 26.5 Alkali Scrubber HCl:<20 mg/Nm3 3 Cl2:<9mg/Nm 3 NH3:<30 mg/Nm Pesticide compound in form of Particulate matter :<20 mg/Nm3 HBr:<5 mg/Nm3 3 Process Stack MPP-7 -- 26.5 Alkali Scrubber HCl:<20 mg/Nm3 3 Cl2:<9mg/Nm 3 NH3:<30 mg/Nm Pesticide compound in form of Particulate matter :<20 mg/Nm3 4 Process Stack MPP-8 -- 26.5 Alkali Scrubber HCl:<20 mg/Nm3 3 Cl2:<9mg/Nm 3 NH3:<30 mg/Nm Pesticide compound in form of Particulate matter :<20 mg/Nm3 5 Process Stack -- 26.5 Alkali Scrubber HCl:<20 mg/Nm3 3 MPP-9/High Pressure NH3:<30 mg/Nm 3 Reaction Plant CH3Cl:<20 mg/Nm
6 Hydrogenation Plant -- 26.5 Automation HC-20 mg/Nm3 (Vent 2 nos.) 7 MEE Process Stack -- 26.5 Hypo scrubber PM: <50 mg/Nm3 followed by alkali HC: <20 mg/Nm3 scrubber
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8 Rotary Kiln -- 30 Ventury Scrubber PM: <50 mg/Nm3 Incinerator followed by Alkali HCl: <50 mg/Nm3 scrubber SO2 :<200 mg/Nm3 3 NOX: <400 mg/Nm Total dioxine and furan: <0.1 ng TEQ/Nm3 Sb+As+Pb+ Cr+CO+Cu+Mn+Ni +V+their compound: <1.5 mg/Nm3 Note: Incinerator Designed is as per CPCB guidelines Process Gas stacks-After Expansion No additional stack invloved. Scrubbers will be modified as per requirement.
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