Manufacturing activities in proposed project including various …environmentclearance.nic.in/writereaddata/Online/TOR/27... · 2017-10-27 · Hexaconazole is isolated from molten

M/s.CRYSTALCROPPROTECTIONPVT.LTD.

Plotno:G-54,MIDCButibori,Nagpur,

Maharashtra,Pincode– 441122

PreparedBy:

VirendraChaudhary

V.P.Technical

CrystalCropProtectionPvt.Ltd.

Nathupur,Distt:Sonepat(Haryana)

Manufacturing activities in proposed

project including various process description,

reaction scheme and material balance

1. Epoxiconazole

Manufacturing process:

Step -1

Fluorobenzene is reacted with chloro acetyl chloride in presence of aluminum chloride and ethylene

dichloride to get 4-fluoro phenacyl chloride.

Step -2

4-Fluoro phenacyl chloride reacted with 1,2,4-triazole in presence of potassium hydroxide and DMF to

give 2-(1H-1,2,4-triazole-1-yl)-4-fluoro acetophenone.

Step -3

2-(1H-1,2,4-Triazole-1-yl)-4-fluoro acetophenone reacted with 2-chloro benzyl chloride and dimethyl

sulphide in presence of potassium hydroxide and solvent DMF to give the final product

EPOXICONAZOLE.

Reaction scheme:

Material balance Epoxyconazole

2. Hexaconazole

Manufacturing Process:

Preparation of Trimethyl sulfonium sulfate

Dimethyl sulfate is charged in dimethyl sulfide at 33 °C to form trimethyl sulfonium sulfate.

2,4 Dichloro valerophenone is reacted with trimethyl sulfonium sulfate in presence of potassium hydroxide

to form Oxirane. Solvent dimethyl sulfide is recovered by distillation and product (oxirane) is separated

from potassium hydrogen sulfate. Water is added to dissolve salt and back extracted with methylene

dichloride and then, aqueous layer is transferred to ETP. 1,2,4 1H-triazole and potassium hydroxide is

charged in DMF and previously prepared oxirane is added at elevated temperature to form hexaconazole.

After completion of reaction, organic phase is separated by filtration. Carbonate sludge is washed with

DMF and collected with organic filtrate. Sludge is transferred to solid waste DMF is distilled out from

reaction mass first at atmospheric distillation and then by vacuum distillation.

Hexaconazole is isolated from molten mass with help of water. Slurry is

filtered, centrifuged and dried.

Reaction scheme:

MATERIAL BALANCE-Hexaconazole Batch size (Final output): 1000 Kg

S.No Name of material Input Qty.

(Kg)

Product

Out put

Qty. (Kg)

Recovery Losses Total

Liquid Others

1 Dimethyl sulfate 482

1000

DMF loss

11488

2 Sodium sulfide 26 DMF Waste water 12

3 DCVP 760 1198.0 9278

4 Pot. Hydroxide 310

5 1,2,4-Triazole 245

6 Pot. carbonate 45

7 DMF 1210

8 Water 8410

1000.0 1198.0 9278.0 12.0

Total 11488 11488

3. Propiconazole


1,2,4-1H-Triazole and potassium hydroxide is charged in DMSO to form potassium salt of 1,2 4- 1H-

triazole. 2-Bromo-methyl-2-[(2,4 dichlorophenyl)-4-propyl]-1,3-dioxolan (bromoketal) is gradually added

to DMSO containing potassium salt of triazole. Temperature is raised and maintained for few hours to

complete the reaction. After completion of reaction solvent is removed by distillation. Residue is washed

with water and then crude propiconazole is distilled to get technical grade propiconazole. Residue is

transferred to ETP

Reaction scheme:

MATERIAL BALANCE-Propiconazole Batch size (Final output): 1000 Kg

S.

No

Name of material Input

Qty. (Kg)

Product

Out put

Qty.

(Kg)


Liquid Others

1 DMSO 1800

1000

DMSO loss

5512

2 Pot. Hydroxide 237 Bromoketal Waste water 20

3 1,2,4-Triazole 265 1210 1480 Residue

4 Bromoketal 1210 DMSO 22

5 Water 2000 1780

1000.0 2990.0 1480.0 42.0

Total 5512 5512

4. Tricyclazole


2-Hydrazino-4-methyl benzothiazol is charged in formic acid at 90-100 °C for 4hours. Temperature is

raised to complete the reaction. After completion of reaction formic acid is distilled out along with some

water. After most of formic acid is distilled out water is charged in to the reactor and residual acid is

neutralized with caustic soda lye slurry is filtered out, centrifuged and dried. Filtrate is sent to ETP.

Reaction scheme:

MATERIAL BALANCE-Tricyclazole Batch size (Final output): 1000 Kg


Qty. (Kg)

Product

Out put

Qty.

(Kg)


Liquid Others

HMBT 960

1000

5930

Formic acid 530 Formic acid Waste water

Caustic lye 40 290 4640 Drying loss

Water 4400 40

1000.0 290.0 4600.0 40.0

Total 5930 5930

5. Clodinofob-propargyl


The R-(+)-2-(4-hydroxy-phenoxy)-propionic acid is dissolved in dimethyl formamide and then charge

potassium carbonate and 2,3-difluoro-5-chloro pyridine (DFCP). The mass is heated and stirred for several

hours to complete the reaction. To the resulting intermediate R-(+)-2-[4-(5-chloro-3-fluoro-pyridin-2-

yloxy)-phenoxy]-propionic acid potassium salt propargyl chloride in toluene is charged in the reaction

mass. Temperature is raised to complete the reaction. Reaction mass is filtered to remove inorganic salt.

DMF and toluene is distilled off from organic mass to get crude Clodinafop Propargyl. Further purification

is done to get technical grade Clodinafop Propargyl. Solvent is recovered from mother liquor.

Reaction scheme:

MATERIAL BALANCE-Clodinofob-propargyl Batch size (Final output): 1000 Kg

S.No Name of material Input Qty.

(Kg)

Product

Out put

Qty. (Kg)


Liquid Others

1 DMF 1889

1000

DMF loss Salt Waste

5481

2 DHPPA 603 DMF 78 1050

3 K2CO3 850 1811 Methanol

Loss

Solvent

Residue

4 DFCP 531 Methanol 48 204

5 Propargyl chloride 289 1100 Aq. Effluent

6 HCl 10 190

7 Methanol 1148

8 Water 161

1000.0 2911 316 1254

Total 5481 5481

6. Penoxsulam


To the mixture of trizolopyrimidine amine, DMSO and pyridine was added substituted benzene sulphonyl

chloride and reaction mixture was stirred for 8h. After completion of reaction DMSO is distilled out

completely. To the crude mixture water was added, stirred and filterted. Filtrate was dried completely to

afford desired product as penoxsulam.

Reaction scheme:

MATERIAL BALANCE-Penoxsulam Batch size (Final output): 1000 Kg

S.

No


Qty. (Kg)

Product

Out put

Qty.

(Kg)


Liquid Others

1 Trizolopyrimidine

amine

404

1000

DMSO loss

4260

2 Sulphonyl chloride 672 DMSO Waste water 90

3 Pyridine 164 1930 1160 Drying loss

4 DMSO 2020 80

5 Water 1000

1000 1930 1160 170

Total 4260 4260

7. Propaquizafop


Thionyl chloride was added to the stirred solution of (R)-2-(4-((6-chloroquinoxalin-2-

yl)oxy)phenoxy)propanoic acid in toluene and stirred for few hours. After completion of reaction toluene

was distilled out. Into this DMF and propan-2-one O-(2-hydroxyethyl) oxime was charged, pyridine was

added slowly into this reaction and stirred for 6h. After completion of reaction DMF was distilled

completely and crude mixture was treated with water. White solid was filtered and dried to get desired

product.

Reaction scheme:

MATERIAL BALANCE-Propaquizafop Batch size (Final output): 1000 Kg

S.

No


Qty. (Kg)

Product

Out put

Qty.

(Kg)


Liquid Others

1 Carboxylic acid 777

1000

Toluene loss

10482

2 Alcohol 265 Toluene Waste water 148

3 Thionyl chloride 269 2960 2300 DMF loss

4 Pyridine 178 DMF 195

5 DMF 3885 3690 Drying loss

6 Toluene 3108 189

7 Water 2000

1000 6650.0 2300 532

Total 10482 10482

8. Quizalofop ethyl


Charge 2,6-dichloro quinaoxaline and potassium carbonate in dimethyl formamide and charge

ethyl(hydroxy phenoxy) propionate. Temperature was raise to complete the reaction. After completion of

reaction, inorganic salt was filtered off. Adjust pH 4.0 with the help of hydrochloric acid to precipitate

inorganic salt from filtrate. Clarify to remove salt. Distill solvent from organic phase. Crystallize crude

using Methanol and water, filter, centrifuge and dry the product.

Reaction Scheme:

MATERIAL BALANCE-Quizalofop ethyl Batch size (Final output): 1000 Kg

S.

No


Qty. (Kg)

Product

Out put

Qty.

(Kg)


Liquid Others

1 DMF 1694

1000

DMF loss

4665

2 Dichloro quinoxaline 585 DMF Water (reuse) 24

3 K2CO3 500 1670 1255 Drying loss

4 Ethyl-2-(4-

hydroxyphenoxy)propi

onate

618 151

5 HCl 9 Inorganic

salt

6 Methanol 1047 565

7 Water 212

1000 1670.0 1255.0 740.0

Total 4665 4665

9. Flubendiamide


Iodo benzoic acid and TEA was dissolved in MDC. Into this thionyl chloride was added and stirred the

mixture for few hour. After completion of reaction MDC and thionyl chloride was distilled completely.

Crude mixture was again dissolved in MDC and flubendamine was added and stirred for 4h. After

completion of reaction MDC was distilled out. Crude mixture was dissolved in THF and mCPBA was

added portion wise and stirred for 2h. After completion of reaction THF is distilled out. Crude reaction

mixture was dissolved in 10% NaHCO3 solution white ppt was filterted off. Residue was washed with

water and dried completely to get desired product as white powder.

Reaction scheme:

MATERIAL BALANCE-Flubendiamide Batch size (Final output): 1000 Kg

S.

No


Qty. (Kg)

Product

Out put

Qty.(Kg)


Liquid Others

1 Acid 618

1000

THF MDC loss

9754

2 Amine 410 3175 122

3 Thionyl chloride 187 MDC Waste water THF loss

4 TEA 159 2350 2800 165

5 MDC 2472 Drying loss

6 mCPBA 568 142

7 THF 3340

8 10% NaHCO3 2000

1000 5525 2800 429

Total 9754 9754

10. Thiamethoxam


The Intermediate 3-methyl-4-nitroimino-1,2,3,6-tetrahydro-1,3,5-oxadiazine (MMTO) is taken in

acetonitrile and is reacted with 3-chloro-5-chloro methylthiazole (CCMT) in presence of K2CO3 under

reflux. After completing the reaction, the mass is cooled and the product is crystallized, filtered. The

mother liquor is collected and is sent for solvent recovery. The solid product is washed with water and

dried to get the desired product.

Reaction scheme:

MATERIAL BALANCE-Thiamethoxam Batch size (Final output): 1000 Kg

S.

No


Qty. (Kg)

Product

Out put

Qty.(Kg)


Liquid Others

1 CCMT 840

1090

Reaction mass DMF loss

11950

2 MNIO 800 3325 760

3 K2CO3 760 Crude

thiamethoxam

Aq.

effluent

4 DMF 2925 1750 3650

5 Reaction mass 3325 Methanol

6 Water 1775 1375

7 Crude thiamethoxam 1750

8 80% MeOH 1775

1090 6450 3650 760

Total 11950 11950

11.Tebuconazole

ProcessDescription:

Step-1

1-(4-Chlorophenyl)-4,4-Dimethyl-3-Pentanone is reacted with Sodium methoxide inDimethyl

Sulfideandtolueneat40–45°Ctemperatureandcookedtillthereactioniscomplete.DMSis

distilledoutand2-[2-(4-Chlorophenyl)ethyl]-2-(1,1–Dimethylethyl)Oxiraneiscollected

asanintermediate.

Step-2

TheOxiraneintermediateisreactedwith1,2,4-TriazoleinpresenceofDMFat135–140°Ctogetthecrudeproduct.

Step-3

DMF is distilled out under vacuum and the reaction mass is taken in water, centrifuged,washedwithwateranddriedtogettechnicalgradeTebuconazole.TheaqueousMLissenttoETP.

ProcessReaction:

MaterialBalance:

MaterialBalanceforTebuconazole

S.No. RawMaterials Input/MTofProduct(KG)

1 1-(4-Chlorophenyl)4-4-Dimethyl-3-Pentanoate 675

2 Sodiummethoxide 162

3 DimethylSulfide 186

4 Toluene 1400

5 1,2,4-Triazole 206

6 DMF 1100

7 Water 1700

Total 5429

S.No.

Output/MTofProduct(KG)

Remarks

Product

Liquid

Effluent

Air

Emission/loss

Recovery

Solid

Waste

1 Tebuconazole - - 1000 - Product

2 Toluene - 40 1360 - Recycle

3 DMF - 30 1070 - Recycle

4 Effluent 1929 - - - ToETP

Total

1929 70 3430 0

5429

12.Azoxystrobin

ProcessDescription:

MMCPOA(Methyl-3-methoxy-2-2-6-chloropyrimidine-4-4-iyl-oxyphenyl-acrylate)andanhydrous

PotassiumcarbonatearechargedinDMF.

Charge2cyanoPhenoltotheabovereactionmass,addcatalyticamountofCuprousChlorideand

heatthereactionmassto100°Cforfewhours.

Filter the reactionmass to remove inorganics and distil out DMF from reactionmass. Add

hexane andwashthereactionmasswithdilutecaustictoremoveunreactedcyanophenolfromthe

reactionmass.

Crystallize the crude with methanol, centrifuge and dry to get technical grade Azoxystrobin as

whitecrystallinesolid.

ReactionScheme

MaterialBalanceforAzoxystrobinS.No. RawMaterials Input/MTofProduct(KG)

1 MMCPOA 880

2 K2CO3 379

3 DMF 2500

4 2CYANOPHENOL 327

5 CuCl2 11

6 CAUSTICSODA 23

7 WATER 500

8 HEXANE 2500

9 METHANOL 2200

Total 9320


S.No.

Product

Liquid

Effluent

AirEmission

/Loss

Recovery

Solid

Waste

Remarks

1 Azoxystrobin - - 1000 - Product

2 DMF - 100 2400 - Recycle

3 AqueousLayer 1000 - - - ToETP

4 METHANOL - 130 2070 - Recycle

5 Hexane - 100 2400 - Recycle

6 InorganicSalts - - - 120 ToIncineration

Total

1000 330 7870 120

9320

13.Pyraclostrobin

ProcessDescription

Step–1

1,4DichloroBenzenereactswith3-ChloroPyrazole inpresenceofcatalyst&solventXylene toform

Intermediate(A)as3-Chloro4-ChloroPhenylPyrazole.

Step-2

2-ChloroBenzylAlcoholreactswithN-MethoxyCarbamatetoformthesecondIntermediate(B),N-

methoxy,N-(2-OxymethylPhenol)Carbamate.

Step-3

Intermediates(A)&(B)thenundergoesCondensationreactioninpresenceofCatalyst&SolventXylene

to give the final product Pyraclostrobin Technical after Filtration, Washing & Drying.Xylene is

recoveredfromtheMLandrecycled.

ReactionScheme

MaterialBalance

14.Picoxystrobin

ProcessDescription

ReactionScheme

MaterialBalance

15.Fluoxastrobin

ProcessDescription:

Step-1

2-HydroxyPhenacylBromide is reactedwithMethoxyAmine inpresenceof catalystaswell asSolvent-

Toluenetoform2-[(1E)-2-Bromo–N-MethoxyEthanimidoyl]Phenolat60–65°C.

Distilouttolueneaftercompletionofreaction.

Step-2

2- [(1E) -2- Bromo–N-MethoxyEthanimidoyl] Phenol reactedwith potassiumTertiary Butoxide

and Tertiary Butyl Nitrate in presence of Butyl Alcohol to form N- Hydroxy –N- Methoxy -1-

Benzofuran-2,3-Diamineat75–80°C.

Step-3

N-Hydroxy–N-Methoxy-1-Benzofuran-2,3-DiamineisreactedwithEthyleneOxideinpresence

ofPotassiumHydroxideat20–25°Ctogive2-[{(3E)-3-Methoxyiaino-1-Benzofuran-2-(3H)–

ylidene}amino}oxy]Ethanol.

Step-4

2- [{(3E) -3-Methoxyamino-1- Benzofuran-2-(3H) –ylidene} amino} oxy] Ethanol undergoes

CyclizationinpresenceofPotassiumHydroxidetoform2-[{(E)5,6–Dihydro1,4,2Dioxazin-3-yl

(methoxyimino)methyl)Phenolat55–60°C.Distiloffn-Butanol.

Step-5

2-[{(E)5,6–Dihydro1,4,2Dioxazin-3-yl(methoxyimino)methyl)Phenolisreactedat80–85°C,

with4,6–Dichloro-5-FluoroPyrimidineinpresenceofPotassiumHydroxideaswellasSolvent–

DimethylFormamidetoform(E)-1-[2-{6-Chloro-5-FluoroPyrimidine-4-yl)oxy}Phenyl]-1-(5,6

Dihydro-1,4,2-Dioxazin-3-yl)–N–Methoxymethanimine.

Step-6

(E)-1-[2-{6-Chloro-5-FluoroPyrimidine-4-yl)oxy}Phenyl]-1-(5,6Dihydro-1,4,2-Dioxazin-3-yl)

–N –Methoxymethanimine is reacted at 60 – 65°C, with O–Chloro Phenol in presence of

PotassiumHydroxideandSolvent–DMFto formfinalproductasFluoxastrobin.DistiloutDMF,

charge water, centrifuge and dry to get Fluoxastrobin technical.

ReactionScheme

Material Balance for Fluoxastrobin

S. No.

Raw Materials

Input/MTof

Product(KG)1 HydroxyPhenylBromide 450

2 MethoxyAmine 100

3 Catalyst 50

4 Toluene 1450

5 PotassiumTertButoxide 233

6 TertButylNitrate 215

7 ButylAlcohol 1600

8 EthyleneOxide 92

9 PotassiumHydroxide 350

10 TrifluoroPyrimidine 345

11 DMF 1200

12 O-Chloro-Phenol 266

13 WaterforWashing 1700

Total 8051

S. No.

Output/MT of Product (KG)

Remarks

Product

Liquid

Air

Emission

Recovery

Solid

1 Fluoxastrobin - - 1000 - Product

2

Aqueous

Layer

2613

-

-

-

ToETP


4 HBr - 170 - ToScrubber

5 Butanol - 150 1450 - Recycle

6

Residue

-

-

-

18

To

Incineration7 DMF - 120 1080 Recycle

Total

2613 590 4830 18

8051

16.Imidacloprid

ProcessDescription:

2–Chloro,5–ChloromethylPyridine(CCMP)isreactedwithN–NitroIminoImidazolidine

(N-NII)inpresenceofSodiumHydroxideandDimethylFormamideassolventat55–60°C.

After completion of the reaction the slurry is filtered to remove the salts of Sodium

Chloride(NaCl)etc.

The solvent is then removed by distillation from the reaction mass under vacuum, the

residual mass is diluted with water and the resultant slurry is filtered to remove

Imidacloprid.Thewetcakeiswashedwithwater.AqueouslayerissenttoETP.

Methanol is used to crystallize the product to get Imidacloprid Technical.

Reaction Scheme

MaterialBalance:

MaterialBalanceforImidacloprid

S.No.

RawMaterials

Input/MTofProduct

(MT)1 CCMP 873

2 N-NitroIminoidmmidazolidine(N-NII) 825

3 DMF 2134

4 K2CO3 684

5 Water 1000

6 Methanol 400

Total 5916

S.No.

Output/MTofProduct

Remarks

Product

Liquid

Effluent

Air

Emission/

loss

Recovery

Solid

Waste

1 Imidacloprid - - 1000 - Product


3 DMF - 87 2048 - Recycle

4 Methanol - 40 360 - Recycle

6

Residue

-

-

-

121

To

Incineration

Total

2260 127 3408 121

5916

17.Acetamiprid

ProcessDescription:

N-CyanomethylAcetamidate(NCMA)isreactedwith2-Chloro5-(methylaminomethyl)

Pyridine(CMAMP)inMethanolassolventmediaatasub-atmospherictemperature(10–

15°C).Afterthereactioniscompletedtheproductisfilteredanddriedtoobtaintechnical

gradeproduct.ThemotherliquorisdistilledtorecoverMethanolsolventwhichisthen

recycled.

ReactionScheme

MaterialBalance

MaterialBalanceforAcetamiprid

S.No.

RawMaterials

Input/MTofProduct

(KG)

1 NCMA 520

2 CMAMP 700

3 Methanol 1950

Total 3170

S.No.


Remarks

Product

Liquid

Effluent

Air

Emission/

Recovery

Solid

Waste1 Acetamiprid - - 1000 - Product

2

Methanol

-

50

2043

-

Recycle

(Also

includes

byproduct

methanol

3

Residue

-

-

-

77

To

Incineratio

n

Total

- 50 3043 77

3170

18.PyrazosulfuronEthyl

ProcessDescription:

Ethyl-1-methyl-5-Sulfenamide-isocyanate-1H-pyrazole-4-carboxylateisreactedwith2-amino-

4,6- dimethoxy pyrimidine in presence of toluene in a reactor under stirring. Mass is

cooked for 2hoursat85-90°C.

Then, cool themass and centrifuge it. Dry the cake to get technical grade Pyrazosulfuron

Ethylproduct.RecoverthetoluenefromtheMLbydistillation.

ReactionScheme

MaterialBalance

MaterialBalanceforPyrazosulfuronEthyl


1 Pyrazole 668

2 Pyrimidine 435

3 Toluene 1300

Total 2403

S.No.


Remarks

Product

Liquid

Effluent

Air

Emission

Recovery

Solid

Waste1 Pyrazosulfuron - - 1000 - Product


3 Residue - - - 80 ForIncineration

4 DryingLoss

-23 - - Toatmosphere

Total

0 83 2240 80

2403

19.Cymoxanil

ProcessDescription:

Step-1:

1-cyanoacetyl-3-ethyl urea and sodium nitrite solution (40%) are added sequentially into

thereactorcontainingwater.Thereactionisallowedtotakeplaceatcontrolledtemperature

of40–

45°Candthereactionmassisheldatthistemperaturetillcompletionofthe

reaction.Thereactionmassisthencooledtoroomtemperature.

Step-2:

Afterthereactionmassof1ststepiscooledtoroomtemperaturedimethylsulfateisadded

toit.

Thereactionmassisheldat50–55°Ctillcompletionofthereaction.

The reactionmass is then cooled to room temperature and centrifuged. The cake

obtained iswashedwithwateranddriedtogiveCymoxaniltechnical.

ReactionScheme:

MaterialBalance:

MaterialBalanceforCymoxanil


7 1CyanoAcetyl3Ethylurea 834

8 Water 1900

9 SodiumNitrite 353

10 DMSO4 626

Total 3713

S.No.


Remarks

Product

Liquid

Effluent

Air

Emission

Recovery

Solid

Waste1 Cymoxanil - - 1000 - Product


Total

2713 - 1000 -

3713

20.Flonicamid

ReactionScheme:

MaterialBalance:

21.Chlorantraniliprole

ReactionScheme:

MassBalance:

22.Spirotetramat

ProcessDescription

ReactionScheme:

MassBalance:

23.Metamifop

ProcessDescription:

ReactionScheme:

MassBalance:

24. Pyridaben


To the stirred solution of 2-(tert-butyl)-4,5-dichloropyridazin-3(2H)-one in MeOH was added

sodium methoxide and tert-butylphenylmethyl mercaptan and again stir for 2h at 15 °C.

Methanol was recovered and added water white solid was obtain which was further crystalize in

aq. Methanol.

Reaction scheme:

MATERIAL BALANCE- Pyridaben Batch size (Final output): 1000 Kg

S.

No


Qty. (Kg)

Product

Out put

Qty. (Kg)


Liquid Others

1 2-(tert-butyl)-4,5-

dichloropyridazin-3(2H)one

605

1000

MeOH

loss

5450

2 tert-butylphenylmethyl

mercaptan

495 Methanol Aq.

Waste

75

3 NaOMe 150 1425 2900 Drying

loss

4 MeOH 1500 50

5 Water 2000

6 Aq. MeOH 700

1000.0 1425.0 2900.0 125.0 5450

Total 5450

25. Oxadiazon


Reaction was carried out in toluene in presence of NaOMe. Reaction was carried at 100 °C for

6h and then reaction mixture was cooled to room temperature and toluene was recovered. Crude

product was crystallize in MeOH:H2O and then filtered off. White solid was dried completely to

get oxadiazon as desired product.

Reaction scheme:

MATERIAL BALANCE- Oxidiazon Batch size (Final output): 1000 Kg

S.No Name of material Input

Qty.

(Kg)

Product

Qty. (Kg)


Liquid Others

1 Hydrazine carboxylate 1092.8

1000

Toluene

loss

5249

2 Sodium methoxide 156.4 Toluene Aqueous waste 150

3 Toluene 3000 2850 1149

4 MeOH 800

5 Water 200 Drying

loss

100

1000.0 2850.0 3053.0 250.0

Total 5249 5249

26. Clothianidin


Aqueous MeNH2 in MeOH was added in the nitramide intermediate and heated at 55 °C for 4h.

Reaction mixture was cooled to 10 °C to crystallize the product and then filtered. Solid was dried

to get clothianidin technical.

Reaction Scheme:

MATERIAL BALANCE- Clothianidin Batch size (Final output): 1000 Kg

S.No Name of material Input

Qty.

(Kg)

Product

Qty. (Kg)


Liquid Others

1 Nitramide 1220

1000

2480

2 Aq. MeNH2 260 800 Aqueous waste

3 MeOH 1000 600

Drying

loss

80

1000.0 800 600 80.0

Total 2480 2480

27. Metiram

Manufacturing process

1st Step: Ethylene diamine and water are charged under stirring condition and added aqueous

ammonia solution and temperature is raised to about 45-50 °C. Now CS2 is added under reflux. So

that pH of the mass is maintained around 10. The mass is kept under these conditions for 6 to 8 h till

the reaction is complete. Reaction mass of the above reaction was charge within 1 and half hour. Then

reaction mass was allowed to settle. The slurry is get filtered under vacuum to get wet cake of

Metiram intermediate.

2nd

Step: Intermediate react with zinc sulphate and hydrogen peroxide under stirring condition. After

30 minutes’ interval, left over mass of is added and maintain for 1 h. At the temperature of 10-20 °C,

slurry is dried using spray drier to get Metiram as desired product.

Chemical reaction

Step-1

H2O

C2H8N2 + 2CS2 + 2 NH4OH C4H14 N4S4 + 2H2O

60 2*76 2*35 246 2*18

Step- 2

4C4H14 N4S4 + 3ZnSO4 + 4H2O + H2O2

4*246 3* 161.5 4*18 34

(C16H33N11S16Zn3)n + 5NH4OH + 3H2SO4 + H2O

1088 5*35 3*98 18

Mass balance

Material Balance-Metiram Batch size (Final output):1000 Kg

S. No. Name of material Input

Qty(Kg)

Product

output

Qty.(Kg)

Recovery

(Kg)

Losses (Kg) Total

liquid other

1. Ethylene di amine 275.73 CS2 Waste

water

Filtration

loss

5567.52

2. Water 200

3. Aq. ammonia 25% 1608.4 72 4145.52 350

4. Carbon disulfide 768.36 1000

5. Zinc sulphate 2371.29

6. Hydrogen

peroxide 50%

343.74

Total 5567.52 5567.52

28. Mandipropamid


Step-1: 4-Chloromandilic acid, is taken in toluene and is reacted with Thionyl chloride, evolved gases

are removed by nitrogen purging.

Step-2: The acid chloride is coupled with 3,4-Dichloro-5-fluoro-1,1-Biphenyl]-2-amine at room

temperature and the product is filtered, washed and dried to get the intermediate.

Step-3: The Intermediate substitution with 2-propinyl methanesulfonate at room temperature Filter

and the product is filtered, washed and dried to get the desired product.

Chemical reaction:

Cl

OH

O

OH+ S O

Cl

Cl Cl

OH

O

Cl

+ SO

O+ H Cl

OH

O

Cl

Cl

+

OH

O CH3

NH2

OH

O

NHCl

O CH3

OH

+ H Cl

OH

O

NHCl

O CH3

OH

+ CH3 S

O

O

O CH

O

O

NHCl

OCH3

O

CH

CH

+CH3 S

O

O

OH

Chloro mandilic acid186.59

Thionyl chloride119

DMF

Acid chloride205

Sulfer dioxide64

Hydrochloric acid36.5

Acid chloride 205

Hydroxy methoxy phenethylamine167.2

Intermediate335.7


Itermediate335.7

2-propinyl methanesulfonate134

Mandipropamid411.8

Methane sulfonic acid96

Mass balance

Material Balance-Mandipropamid Batch size (Final output):1000 Kg


Qty (Kg)

Product

output

Qty.(Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Others

1. 4-chloromandilic

acid

607.7 Toluene Thionyl

chloride

SO2

4261.96

1620 32.57 208.5

2. Thionyl chloride 407.3

3. DMF 6.07 DMF Toluene HCL

4. toluene 1800 1000

5. 3-methoxy

phenethylamine

544.78 5kg 180 215.92

Methane

sulfonic

acid

Organic

waste

6. 2-propinyl

methanesulfonate

896.11 416.82

583.15

Total 4261.96 4261.96

29. Bixafen


Step-1: 3-(Difluoromethyl)-1-methyl-1-H-pyrazol-4-carboxylic acid, is taken in toluene and is

reacted with Thionyl chloride, evolved gases are removed by nitrogen purging.


temperature and the product is filtered, washed and dried to get the desired product.

Chemical reaction

N

N

CH3

F F

O

OH

+ S

Cl

Cl

ON

N

CH3

F F

O

Cl

+ S

O

O+ H Cl

N

N

CH3

F F

O

Cl

+ NH2

F

Cl

Cl

NN

CH3

F

F O

NH

F

Cl

Cl

+ H Cl

Carboxylic acid176.2

thionyl chloride119

Acid chloride194.5

sulfer dioxide64


Di chloro fluoro biphenyl amine256.1

Bixafen 414

Acid chloride194.5


Mass Balance

Material Balance-Bixafen Batch size (Final output):1000 Kg


Qty(Kg)

Product

output

Qty.(Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Others

1. Carboxylic acid 500.7 Toluene Thionyl

chloride

SO2

3503.03

1350 16.84 181.86

2. Thionyl chloride 355

3. DMF 5 Toluene HCL

4. toluene 1500 1000

5. Dichlorofluoro

biphenyl amine

742.33 150 207.4

Organic

waste

Aqueous

waste

6. Potassium

carbonate

400 195.72 401.21

Total 3503.03 3503.03

30. Fluxapyroxad




Step-2: The acid chloride is coupled with 3,4,5-trifluoro-2-aminobiphenyl at room temperature and

the product is filtered, washed and dried to get the desired product.

Chemical Reaction

NN

F

F

CH3

O

OH

+ S O

Cl

Cl

NN

F

F

CH3

O

Cl

+ S

O

O

+ H Cl


Thionyl chloride119

Acid chloride194.5

Sulfer dioxide64

Hydrochloride36.5

NN

F

F

CH3

O

Cl

+

F

FF

NH2 N

N

FF

CH3

O

NH

F

F

F

+

3,4,5-Trifluoro-2-aminobiphenyl223.19

Fluxapyroxad381.3

H Cl

Hydrochloride36.5

Acid chloride194.5

DMF

K2CO3

Material Balance-Fluxapyroxad Batch size (Final output):1000 Kg


Qty(Kg)

Product

output

Qty.(Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Others


chloride

SO2

3745.92

1498 19.02 201.42


3. DMF 5.54 Toluene HCL

4. toluene 1664 1000

5. 3,4,5-trifloro-2-

aminobiphenyl

702.40 166 227.53

Organic

waste

Aqueous

waste

6. Potassium

carbonate

425.7 190.25 443.7

Total !"#$.!" 3745.92

31. Sulfoxaflor


Sulfilimine dissolve in ethylene dichloride and added sodium permanganate at 0-5 °C digest

for 4-5 h. After 5 h added sodium bisulphite dissolve in water at room temperature maintain for

5-6 h and the product is filtered, washed and dried to get the desired product.

Chemical Reaction

N

S

CH3

N

CH3

F

F

F

N

+O Mn

5-

O

O

O Na

N

S

CH3

N

CH3

F

FF

N

O

sulfilimine261.27

sodium permagnate142

Na2S2O7

Sulfoxaflor277.27

Mass Balance

Material Balance- Sulfoxaflor Batch size (Final output):1000 Kg


Qty(Kg)

Product

output

Qty.(Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Other

1. Sulfilimine 1070 EDC EDC Vapour

loss

Aqueous

waste

14200.6

6

4922

428 7850.66

2. Sodium

permanganate

581.97

3. Ethylene dichloride 5350

4. Sodium bisulphite 778.69 1000

5. Water 6420

Total !"#$$.!! 14200.6

6

32. Benzovindiflupyr

Manufacturing Process

Step-1: 3-(Difluoromethyl)-1-methyl-1-H-pyrazol-4-carboxylic acid, is taken in ethylene dichloride

and is reacted with Thionyl chloride, evolved gases are removed by nitrogen purging.

Step-2: The acid chloride is coupled with 1, 2,3, 4-tetrahydro-1,4-methanonaphthalen-5-amine

at room temperature and the product is filtered, washed and dried to get the desired product.

Chemical reaction:

N

N

CH3

O

OH

F

F

+ S

O

Cl Cl

NN

CH3

O

Cl

F

F

+

Step-1

Step-2

NN

CH3

O

Cl

F

F

+

NH2

Cl

Cl

NN

NH

O

CH3

F

F Cl

Cl

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Mass: 176.12

sulfurous dichloride

Mass: 118.97

DMF

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride

Mass: 194.56

Mass: 36.46


Mass: 194.56

9-(dichloromethylidene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-amine

Mass: 240.13Mass: 398.23

N-[9-(dichloromethylidene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide

+ ClH

Mass: 36.46

ClH + S

O

OSulferdioxide64

Mass Balance

MATERIAL BALANCE- Benzovindiflupyr Batch size (Final output): 1000 Kg

S.

No.

Name of

Material

Input

Qty.

(Kg)

Products

out put

Qty. (Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Others

4709.58

1. EDC 1672

1000

EDC EDC

vapour

loss

HCL

2. Carboxylic acid 557.33 1505

115.5

3. DMF 5.57

4. Triethylamine 320.28 167 SO2

5. SOCl2 395.40

6. DCMTMPA 759.00 202.5

7. Water 1000

Aqueous

waste

1719.58

Total 4709.58 4709.58

33. FLUOPRAM TECHNICAL


Step-1: 2-(Trifluoromethyl) benzoic acid (TFBC), is taken in ethylene dichloride and is reacted with

Thionyl chloride, evolved gases are removed by nitrogen purging.

Step-2: 3-chloro-5-(trifluoromethyl)-2-ethylacetamide-pyridinyl with water under stirrer heat reaction

mass at 40-45°C. Started addition of hydrochloric acid in two hours.

Reaction mass heat up to reflux for 3-4 hours. Cool to 30°C, added two times EDC in mass under

stirrer for one hour, reaction mass taken for layer separation, organic layer concentrate under vacuum

distillation. Obtained crude material taken for next step.

Step-3: The acid chloride is coupled with Intermediate at room temperature and the product is

filtered, washed and dried to get the desired product.

Chemical reaction:

FF

F

O

OH

+

F F

F

O

ClS

OO+S

O

ClCl

Step-1

Step-2

F

FF O

Cl

+

N

F

F

FCl

NH

OCH3

ON

F

FF Cl

NH

F

FF

ClHOH2 N

F

F

F

Cl

NH2

+CH3

O

OH

+ N

F

F

F

Cl

NH2

+ ClH

Step-3

+ ClH

chloro tri fluro methyl 2-pyridine ethanamine266.64

Acetic acid60.05

Cat

NaOH

Trifluoromethyl banzoic acid190.11

Thionyl chloride119 Acid chloride

208.56

sulpher dioxide64


Acid chloride208.56

Water18 Intermediate

224.61

intermediate224.61

Fluopyram396.71


Mass Balance

MATERIAL BALANCE- Fluopyram Batch size (Final output): 1000 Kg

S.

No

Name of

Material

Input

Qty.

(Kg)

Product

s out put

Qty.

(Kg)

Recovery

Kg

Losses (Kg) Total

Liquid Others

1 EDC

1690

1000

EDC

EDC

vapour

loss

HCL

6147.16

2 DFMPCA 563.64 1555 135 108.21

3 DMF 5.63 Acetic acid SO2

4 SOCl2 370.31 191.04 189.74

5. Chloro

trifluoromethyl

pyridine

ethaneamine

849

Aqueous

waste

6 Hydrochloric

acid 387

2968.17

7 Water 2163

8 Sodium

hydroxide 118.58

Total 6147.16 6147.16

34. Dinetofuron technical


3-Aminomethyl tetrahydrofuron with water under stirrer added sodium hydroxide, sodium chloride

and diethylnitrosourea reaction at 0-5 °C. Maintain for 10 h and the product is filtered, washed and


Chemical Reaction:

O

NH2

+

CH3

N

O

CH3

NH

N O

O

O

N

NH

CH3

NH

N

O

O

+ CH3 OH

3-Amino methyl tetrahydrofuron101.15

Dimethylnitroso urea133.11

NaOH

NaCL

Dinetofuron202.21

Methanol32

Mass balance

Material Balance- Dinetofuron Batch size (Final output): 1000 Kg

S.

No

Name of

Material

Input

Qty.

(Kg)

Product

s out

put Qty.

(Kg)

Recovery

Losses Total

Liquid Others

3463.6

1. 3-Amino methyl

tetrahydrofuron 610.02

1000

Methanol Aqueous

waste

2. Dimethylnitroso

urea 842.87

192.62 2270.94

3. Sodium

hydroxide 237.67

4. Sodium chloride 553

5. Water 1220

Total 3463.56 3463.56

35. Bentazone Technical


2-Amino benzoic acid is charged in to ethylene dichloride and reacted with isopropyl amine

and chlorosulphonic acid at room temperature for 6 h. Washed with water and concentrate

EDC under vacuum and filtered dried to get the desired product.

Chemical Reaction:

NH2 O

OCH3 +

NH2

CH3CH3

+ Cl S

O

O

OH

O

NCH3

NH

S O

O

+ H Cl + CH3 OH + OH2

2-Amino banzoic acid methyl ester151.16

Isopropylamine59.11

chlorosulphonic acid116.5

Bentazone240.27

36.5

3218

Mass Balance

Material Balance- Bantazone Batch size (Final output): 1000 Kg

S.

No

Name of

Material

Input

Qty.

(Kg)

Products

out put

Qty. (Kg)

Recovery

Kg

Losses (Kg) Total

Liquid Others

5396.42

1. Amino benzoic

acid 741

1000

EDC Aqueou

s waste HCL

2. Isopropyl amine 304.22

2045.16

1837.6 178.92

3. Chlorosulphonic

acid

628.20 EDC Methan

ol

4. EDC 2223

177.84 156.9

5. Water 1500

Total 5396.42 5396.42

36. Saflufenacil


2-chloro-5-[2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]-4-fluoro-N[methyl(propan-

2-yl) sulfamoyl]benzamide in to toluene and added catalyst under stirring and added dimethyl

sulphate at room temperature for 3 h and digest 40-45 °C. The desired product is filtered, washed and


Chemical Reaction

NNH

F

F

FO

OF Cl

NH

O

S

O

ON

CH3

CH3CH3

+

O

S

OO

O

CH3CH3

NN

F

F

FO

OF Cl

NH

O

S

O

ON

CH3

CH3CH3

CH3+

CH3 O

SO

O

OH

2-chloro-5-[2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]-4-fluoro-N-[methyl(pr

opan-2-yl)sulfamoyl]benzamide486.82

Dimethyl sulphate126

Saflufenacil501.85

Methyl hydrogen sulfate112

Mass Balance Material Balance- Saflufenacil Batch size (Final output): 1000 Kg

S.

No

Name of

Material

Input Qty.

(Kg)

Products

out put

Qty. (Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Others 5793.66

1. Starting

Material 1143.2

1000

Toluene

Toluene

Vapour

loss

Aqueous

waste

2. Toluene 3429.6 3120.93

308.66 1100.67

3. Dimethyl

sulphate 353

Methyl

hydrogen

Sulphate

4. Catalyst

22.86

5. 10% NaOH

Solution 845 263.4

Total 5793.66 5793.66

37. Clomazone


Charged in reactor ethylene dichloride and 1-chloro-2-(chloromethyl)benzene under stirrer with

triethylamine, isoxazolidinone. Reaction mass maintained at 0 °C for 24 h to give final products of

Clomazone. Acidic water and solvent was recovered to get desired Clomazone technical.

Chemical reaction:

NH

O

CH3

CH3

O

+

Cl

ClN

O

CH3

CH3

OCl

+ ClH

Step-1

Mass: 115.13

4,4-dimethyl-1,2-oxazolidin-3-one

Mass: 161.02

1-chloro-2-(chloromethyl)benzene

Mass: 239.69

2-[(2-chlorophenyl)methyl]-4,4-dimethyl-1,2-oxazolidin-3-one

Mass: 36.46

Mass Balance

MATERIAL BALANCE-Clomazone Batch size (Final output): 1000 Kg

S. No Name of Material Input

Qty. (Kg)

Products

output Qty.

(Kg)

Recovery Losses

Total Liquid Others

1 EDC 3750.87

1000

EDC Water mL EDC

6791.62

2 Isoxazolidinone 600.41 3375.78 1266.52 375.09

3 Dichloromethylben

zene 856.25 TEA HCL

4 Triethylamine 554.09 554.09 190.14

5 Hydrochloric acid 30.00 HCL

6 Water 1000 30.00

Total 6791.62 6791.62

38. Tembortione


Charged in reactor acetonitrile and Benzoic acid Cyclohexen ester under stirrer with triethylamine

Cynoacetone. Reaction mass maintained at 30 °C for 24 h to give final products of Tembortione.

Recovered solvent, given acidic water wash to get crystallized Tembortione technical.

Chemical reaction:

O

O

O

Cl S

O

O

CH3

O

F

FF

O

Cl

S OO

CH3

O

F

F

F

O

O

Mass: 440.81

3-oxocyclohex-1-en-1-yl 2-chloro-4-(methanesulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]benzoate

2-{2-chloro-4-(methanesulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]benzoyl}cyclohexane-1,3-dione

Mass: 440.81

catalyst

Mass Balance

MATERIAL BALANCE- Tembortione Batch size (Final output): 1000 Kg

S.

No Name of Material

Input

Qty. (Kg)

Products

output

Qty. (Kg)

Recovery

Kg

Losses (Kg) Total

Liquid Others

1 ACN 4623.53

1000

ACN Aqueous

waste ACN

7441.16

2 Benzoic

acidcyclohexen 1176.47

3 Cynoacetone 58.82 4161.17 1641.16

462.35 4 Triethylamine 58.82

Organic

waste 5 Hydrochloric acid 23.52

6 Water 1500 176.48

Total 7441.16 7441.16

39. Sulfentrazone technical


2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one in

toluene under stirrer with Methane sulfonyl chloride. Reaction mass maintained at 120 °C for 12 h to

give final products of Sulfentrazone. Recovered half volume of toluene and cool to room temperature

filtered and dried to get final desired compound.

Chemical reaction:

++ ClH

Step-1

Methanesulfonyl chloride114.55

36.46

Cl

Cl

NH2

N

N

N

F

F

CH3

OCH3

S

O

O

Cl

Cl

Cl

NH

N

N

N

F

F

CH3

O

S

O

CH3O

Sulfentrazone387.19

ADMDT309.10

Mass Balance

MATERIAL BALANCE- Sulfentrazone Batch size (Final output): 1000 Kg

S.

No Name of Material

Input

Qty. (Kg)

Products

output

Qty. (Kg)

Recovery Losses

Total Liquid Others

1 Toluene 3990.28

1000

Toluene Toluene Organic

waste

5293.87

2 ADMDT

939.19

3591.25

399.02 205.81

3 Methane sulfonyl

chloride 355.02

Triphen

ylphosp

hine

HCL

4 Triphenylphosphine 9.38

9.38

88.41

Total 5293.87 5293.87

27. Metiram


1st Step: Ethylene diamine and water are charged under stirring condition and added aqueous

ammonia solution and temperature is raised to about 45-50 °C. Now CS2 is added under reflux. So

that pH of the mass is maintained around 10. The mass is kept under these conditions for 6 to 8 h till

the reaction is complete. Reaction mass of the above reaction was charge within 1 and half hour. Then

reaction mass was allowed to settle. The slurry is get filtered under vacuum to get wet cake of

Metiram intermediate.

2nd

Step: Intermediate react with zinc sulphate and hydrogen peroxide under stirring condition. After

30 minutes’ interval, left over mass of is added and maintain for 1 h. At the temperature of 10-20 °C,

slurry is dried using spray drier to get Metiram as desired product.

Chemical reaction

Step-1

H2O

C2H8N2 + 2CS2 + 2 NH4OH C4H14 N4S4 + 2H2O

60 2*76 2*35 246 2*18

Step- 2

4C4H14 N4S4 + 3ZnSO4 + 4H2O + H2O2

4*246 3* 161.5 4*18 34

(C16H33N11S16Zn3)n + 5NH4OH + 3H2SO4 + H2O

1088 5*35 3*98 18

Mass balance

Material Balance-Metiram Batch size (Final output):1000 Kg


Qty(Kg)

Product

output

Qty.(Kg)

Recovery

(Kg)

Losses (Kg) Total

liquid other

1. Ethylene di amine 275.73 CS2 Waste

water

Filtration

loss

5567.52

2. Water 200

3. Aq. ammonia 25% 1608.4 72 4145.52 350

4. Carbon disulfide 768.36 1000

5. Zinc sulphate 2371.29

6. Hydrogen

peroxide 50%

343.74

Total 5567.52 5567.52

28. Mandipropamid


Step-1: 4-Chloromandilic acid, is taken in toluene and is reacted with Thionyl chloride, evolved gases

are removed by nitrogen purging.


temperature and the product is filtered, washed and dried to get the intermediate.

Step-3: The Intermediate substitution with 2-propinyl methanesulfonate at room temperature Filter

and the product is filtered, washed and dried to get the desired product.

Chemical reaction:

Cl

OH

O

OH+ S O

Cl

Cl Cl

OH

O

Cl

+ SO

O+ H Cl

OH

O

Cl

Cl

+

OH

O CH3

NH2

OH

O

NHCl

O CH3

OH

+ H Cl

OH

O

NHCl

O CH3

OH

+ CH3 S

O

O

O CH

O

O

NHCl

OCH3

O

CH

CH

+CH3 S

O

O

OH

Chloro mandilic acid186.59

Thionyl chloride119

DMF

Acid chloride205

Sulfer dioxide64


Acid chloride 205

Hydroxy methoxy phenethylamine167.2

Intermediate335.7


Itermediate335.7

2-propinyl methanesulfonate134

Mandipropamid411.8

Methane sulfonic acid96

Mass balance

Material Balance-Mandipropamid Batch size (Final output):1000 Kg


Qty (Kg)

Product

output

Qty.(Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Others

1. 4-chloromandilic

acid

607.7 Toluene Thionyl

chloride

SO2

4261.96

1620 32.57 208.5


3. DMF 6.07 DMF Toluene HCL

4. toluene 1800 1000

5. 3-methoxy

phenethylamine

544.78 5kg 180 215.92

Methane

sulfonic

acid

Organic

waste

6. 2-propinyl

methanesulfonate

896.11 416.82

583.15

Total 4261.96 4261.96

29. Bixafen





temperature and the product is filtered, washed and dried to get the desired product.

Chemical reaction

N

N

CH3

F F

O

OH

+ S

Cl

Cl

ON

N

CH3

F F

O

Cl

+ S

O

O+ H Cl

N

N

CH3

F F

O

Cl

+ NH2

F

Cl

Cl

NN

CH3

F

F O

NH

F

Cl

Cl

+ H Cl


thionyl chloride119

Acid chloride194.5

sulfer dioxide64


Di chloro fluoro biphenyl amine256.1

Bixafen 414

Acid chloride194.5


Mass Balance

Material Balance-Bixafen Batch size (Final output):1000 Kg


Qty(Kg)

Product

output

Qty.(Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Others


chloride

SO2

3503.03

1350 16.84 181.86

2. Thionyl chloride 355

3. DMF 5 Toluene HCL

4. toluene 1500 1000

5. Dichlorofluoro

biphenyl amine

742.33 150 207.4

Organic

waste

Aqueous

waste

6. Potassium

carbonate

400 195.72 401.21

Total 3503.03 3503.03

30. Fluxapyroxad




Step-2: The acid chloride is coupled with 3,4,5-trifluoro-2-aminobiphenyl at room temperature and

the product is filtered, washed and dried to get the desired product.

Chemical Reaction

NN

F

F

CH3

O

OH

+ S O

Cl

Cl

NN

F

F

CH3

O

Cl

+ S

O

O

+ H Cl


Thionyl chloride119

Acid chloride194.5

Sulfer dioxide64

Hydrochloride36.5

NN

F

F

CH3

O

Cl

+

F

FF

NH2 N

N

FF

CH3

O

NH

F

F

F

+

3,4,5-Trifluoro-2-aminobiphenyl223.19

Fluxapyroxad381.3

H Cl

Hydrochloride36.5

Acid chloride194.5

DMF

K2CO3

Material Balance-Fluxapyroxad Batch size (Final output):1000 Kg


Qty(Kg)

Product

output

Qty.(Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Others


chloride

SO2

3745.92

1498 19.02 201.42


3. DMF 5.54 Toluene HCL

4. toluene 1664 1000

5. 3,4,5-trifloro-2-

aminobiphenyl

702.40 166 227.53

Organic

waste

Aqueous

waste

6. Potassium

carbonate

425.7 190.25 443.7

Total !"#$.!" 3745.92

31. Sulfoxaflor


Sulfilimine dissolve in ethylene dichloride and added sodium permanganate at 0-5 °C digest

for 4-5 h. After 5 h added sodium bisulphite dissolve in water at room temperature maintain for

5-6 h and the product is filtered, washed and dried to get the desired product.

Chemical Reaction

N

S

CH3

N

CH3

F

F

F

N

+O Mn

5-

O

O

O Na

N

S

CH3

N

CH3

F

FF

N

O

sulfilimine261.27

sodium permagnate142

Na2S2O7

Sulfoxaflor277.27

Mass Balance

Material Balance- Sulfoxaflor Batch size (Final output):1000 Kg


Qty(Kg)

Product

output

Qty.(Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Other

1. Sulfilimine 1070 EDC EDC Vapour

loss

Aqueous

waste

14200.6

6

4922

428 7850.66

2. Sodium

permanganate

581.97

3. Ethylene dichloride 5350

4. Sodium bisulphite 778.69 1000

5. Water 6420

Total !"#$$.!! 14200.6

6

32. Benzovindiflupyr


Step-1: 3-(Difluoromethyl)-1-methyl-1-H-pyrazol-4-carboxylic acid, is taken in ethylene dichloride

and is reacted with Thionyl chloride, evolved gases are removed by nitrogen purging.

Step-2: The acid chloride is coupled with 1, 2,3, 4-tetrahydro-1,4-methanonaphthalen-5-amine

at room temperature and the product is filtered, washed and dried to get the desired product.

Chemical reaction:

N

N

CH3

O

OH

F

F

+ S

O

Cl Cl

NN

CH3

O

Cl

F

F

+

Step-1

Step-2

NN

CH3

O

Cl

F

F

+

NH2

Cl

Cl

NN

NH

O

CH3

F

F Cl

Cl

3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

Mass: 176.12

sulfurous dichloride

Mass: 118.97

DMF


Mass: 194.56

Mass: 36.46


Mass: 194.56

9-(dichloromethylidene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-amine

Mass: 240.13Mass: 398.23

N-[9-(dichloromethylidene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide

+ ClH

Mass: 36.46

ClH + S

O

OSulferdioxide64

Mass Balance

MATERIAL BALANCE- Benzovindiflupyr Batch size (Final output): 1000 Kg

S.

No.

Name of

Material

Input

Qty.

(Kg)

Products

out put

Qty. (Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Others

4709.58

1. EDC 1672

1000

EDC EDC

vapour

loss

HCL

2. Carboxylic acid 557.33 1505

115.5

3. DMF 5.57

4. Triethylamine 320.28 167 SO2

5. SOCl2 395.40

6. DCMTMPA 759.00 202.5

7. Water 1000

Aqueous

waste

1719.58

Total 4709.58 4709.58

33. FLUOPRAM TECHNICAL


Step-1: 2-(Trifluoromethyl) benzoic acid (TFBC), is taken in ethylene dichloride and is reacted with

Thionyl chloride, evolved gases are removed by nitrogen purging.

Step-2: 3-chloro-5-(trifluoromethyl)-2-ethylacetamide-pyridinyl with water under stirrer heat reaction

mass at 40-45°C. Started addition of hydrochloric acid in two hours.

Reaction mass heat up to reflux for 3-4 hours. Cool to 30°C, added two times EDC in mass under

stirrer for one hour, reaction mass taken for layer separation, organic layer concentrate under vacuum

distillation. Obtained crude material taken for next step.

Step-3: The acid chloride is coupled with Intermediate at room temperature and the product is

filtered, washed and dried to get the desired product.

Chemical reaction:

FF

F

O

OH

+

F F

F

O

ClS

OO+S

O

ClCl

Step-1

Step-2

F

FF O

Cl

+

N

F

F

FCl

NH

OCH3

ON

F

FF Cl

NH

F

FF

ClHOH2 N

F

F

F

Cl

NH2

+CH3

O

OH

+ N

F

F

F

Cl

NH2

+ ClH

Step-3

+ ClH

chloro tri fluro methyl 2-pyridine ethanamine266.64

Acetic acid60.05

Cat

NaOH

Trifluoromethyl banzoic acid190.11

Thionyl chloride119 Acid chloride

208.56

sulpher dioxide64


Acid chloride208.56

Water18 Intermediate

224.61

intermediate224.61

Fluopyram396.71


Mass Balance

MATERIAL BALANCE- Fluopyram Batch size (Final output): 1000 Kg

S.

No

Name of

Material

Input

Qty.

(Kg)

Product

s out put

Qty.

(Kg)

Recovery

Kg

Losses (Kg) Total

Liquid Others

1 EDC

1690

1000

EDC

EDC

vapour

loss

HCL

6147.16

2 DFMPCA 563.64 1555 135 108.21

3 DMF 5.63 Acetic acid SO2

4 SOCl2 370.31 191.04 189.74

5. Chloro

trifluoromethyl

pyridine

ethaneamine

849

Aqueous

waste

6 Hydrochloric

acid 387

2968.17

7 Water 2163

8 Sodium

hydroxide 118.58

Total 6147.16 6147.16

34. Dinetofuron technical


3-Aminomethyl tetrahydrofuron with water under stirrer added sodium hydroxide, sodium chloride

and diethylnitrosourea reaction at 0-5 °C. Maintain for 10 h and the product is filtered, washed and


Chemical Reaction:

O

NH2

+

CH3

N

O

CH3

NH

N O

O

O

N

NH

CH3

NH

N

O

O

+ CH3 OH

3-Amino methyl tetrahydrofuron101.15

Dimethylnitroso urea133.11

NaOH

NaCL

Dinetofuron202.21

Methanol32

Mass balance

Material Balance- Dinetofuron Batch size (Final output): 1000 Kg

S.

No

Name of

Material

Input

Qty.

(Kg)

Product

s out

put Qty.

(Kg)

Recovery

Losses Total

Liquid Others

3463.6

1. 3-Amino methyl

tetrahydrofuron 610.02

1000

Methanol Aqueous

waste

2. Dimethylnitroso

urea 842.87

192.62 2270.94

3. Sodium

hydroxide 237.67

4. Sodium chloride 553

5. Water 1220

Total 3463.56 3463.56

35. Bentazone Technical


2-Amino benzoic acid is charged in to ethylene dichloride and reacted with isopropyl amine

and chlorosulphonic acid at room temperature for 6 h. Washed with water and concentrate

EDC under vacuum and filtered dried to get the desired product.

Chemical Reaction:

NH2 O

OCH3 +

NH2

CH3CH3

+ Cl S

O

O

OH

O

NCH3

NH

S O

O

+ H Cl + CH3 OH + OH2

2-Amino banzoic acid methyl ester151.16

Isopropylamine59.11

chlorosulphonic acid116.5

Bentazone240.27

36.5

3218

Mass Balance

Material Balance- Bantazone Batch size (Final output): 1000 Kg

S.

No

Name of

Material

Input

Qty.

(Kg)

Products

out put

Qty. (Kg)

Recovery

Kg

Losses (Kg) Total

Liquid Others

5396.42

1. Amino benzoic

acid 741

1000

EDC Aqueou

s waste HCL

2. Isopropyl amine 304.22

2045.16

1837.6 178.92

3. Chlorosulphonic

acid

628.20 EDC Methan

ol

4. EDC 2223

177.84 156.9

5. Water 1500

Total 5396.42 5396.42

36. Saflufenacil


2-chloro-5-[2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]-4-fluoro-N[methyl(propan-

2-yl) sulfamoyl]benzamide in to toluene and added catalyst under stirring and added dimethyl

sulphate at room temperature for 3 h and digest 40-45 °C. The desired product is filtered, washed and


Chemical Reaction

NNH

F

F

FO

OF Cl

NH

O

S

O

ON

CH3

CH3CH3

+

O

S

OO

O

CH3CH3

NN

F

F

FO

OF Cl

NH

O

S

O

ON

CH3

CH3CH3

CH3+

CH3 O

SO

O

OH

2-chloro-5-[2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]-4-fluoro-N-[methyl(pr

opan-2-yl)sulfamoyl]benzamide486.82

Dimethyl sulphate126

Saflufenacil501.85

Methyl hydrogen sulfate112

Mass Balance Material Balance- Saflufenacil Batch size (Final output): 1000 Kg

S.

No

Name of

Material

Input Qty.

(Kg)

Products

out put

Qty. (Kg)

Recovery

(Kg)

Losses (Kg) Total

Liquid Others 5793.66

1. Starting

Material 1143.2

1000

Toluene

Toluene

Vapour

loss

Aqueous

waste

2. Toluene 3429.6 3120.93

308.66 1100.67

3. Dimethyl

sulphate 353

Methyl

hydrogen

Sulphate

4. Catalyst

22.86

5. 10% NaOH

Solution 845 263.4

Total 5793.66 5793.66

37. Clomazone


Charged in reactor ethylene dichloride and 1-chloro-2-(chloromethyl)benzene under stirrer with

triethylamine, isoxazolidinone. Reaction mass maintained at 0 °C for 24 h to give final products of

Clomazone. Acidic water and solvent was recovered to get desired Clomazone technical.

Chemical reaction:

NH

O

CH3

CH3

O

+

Cl

ClN

O

CH3

CH3

OCl

+ ClH

Step-1

Mass: 115.13

4,4-dimethyl-1,2-oxazolidin-3-one

Mass: 161.02

1-chloro-2-(chloromethyl)benzene

Mass: 239.69

2-[(2-chlorophenyl)methyl]-4,4-dimethyl-1,2-oxazolidin-3-one

Mass: 36.46

Mass Balance

MATERIAL BALANCE-Clomazone Batch size (Final output): 1000 Kg

S. No Name of Material Input

Qty. (Kg)

Products

output Qty.

(Kg)

Recovery Losses

Total Liquid Others

1 EDC 3750.87

1000

EDC Water mL EDC

6791.62

2 Isoxazolidinone 600.41 3375.78 1266.52 375.09

3 Dichloromethylben

zene 856.25 TEA HCL

4 Triethylamine 554.09 554.09 190.14

5 Hydrochloric acid 30.00 HCL

6 Water 1000 30.00

Total 6791.62 6791.62

38. Tembortione


Charged in reactor acetonitrile and Benzoic acid Cyclohexen ester under stirrer with triethylamine

Cynoacetone. Reaction mass maintained at 30 °C for 24 h to give final products of Tembortione.

Recovered solvent, given acidic water wash to get crystallized Tembortione technical.

Chemical reaction:

O

O

O

Cl S

O

O

CH3

O

F

FF

O

Cl

S OO

CH3

O

F

F

F

O

O

Mass: 440.81

3-oxocyclohex-1-en-1-yl 2-chloro-4-(methanesulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]benzoate

2-{2-chloro-4-(methanesulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]benzoyl}cyclohexane-1,3-dione

Mass: 440.81

catalyst

Mass Balance

MATERIAL BALANCE- Tembortione Batch size (Final output): 1000 Kg

S.

No Name of Material

Input

Qty. (Kg)

Products

output

Qty. (Kg)

Recovery

Kg

Losses (Kg) Total

Liquid Others

1 ACN 4623.53

1000

ACN Aqueous

waste ACN

7441.16

2 Benzoic

acidcyclohexen 1176.47

3 Cynoacetone 58.82 4161.17 1641.16

462.35 4 Triethylamine 58.82

Organic

waste 5 Hydrochloric acid 23.52

6 Water 1500 176.48

Total 7441.16 7441.16

39. Sulfentrazone technical


2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one in

toluene under stirrer with Methane sulfonyl chloride. Reaction mass maintained at 120 °C for 12 h to

give final products of Sulfentrazone. Recovered half volume of toluene and cool to room temperature

filtered and dried to get final desired compound.

Chemical reaction:

++ ClH

Step-1

Methanesulfonyl chloride114.55

36.46

Cl

Cl

NH2

N

N

N

F

F

CH3

OCH3

S

O

O

Cl

Cl

Cl

NH

N

N

N

F

F

CH3

O

S

O

CH3O

Sulfentrazone387.19

ADMDT309.10

Mass Balance

MATERIAL BALANCE- Sulfentrazone Batch size (Final output): 1000 Kg

S.

No Name of Material

Input

Qty. (Kg)

Products

output

Qty. (Kg)

Recovery Losses

Total Liquid Others

1 Toluene 3990.28

1000

Toluene Toluene Organic

waste

5293.87

2 ADMDT

939.19

3591.25

399.02 205.81

3 Methane sulfonyl

chloride 355.02

Triphen

ylphosp

hine

HCL

4 Triphenylphosphine 9.38

9.38

88.41

Total 5293.87 5293.87

40. Lambda Cyhalothrin technical

41. Bifenthrin Technical

42. Cypermethrin Technical

Reaction Scheme

Documents

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