1929-82-4

Basic information

• Product Name: Nitrapyrin
• Synonyms: NITRAPYRIN;N-SERVE;IFLAB-BB F0848-0285;NITRAPYRIN PESTANAL;NITRAPYRIN, 100MG, NEAT;1,4-DIOXAN DRIED, (MAX. 0,005 % H2O), R. G., STABILIZED;nitrapyrin (bsi,iso,ansi);NITRADYRIN
• CAS NO: 1929-82-4
• Molecular Formula: C₆H₃Cl₄N
• Molecular Weight: 230.91
• EINECS: 217-682-2
• Product Categories: Organics;Pyridine;Building Blocks;C5 to C6;C6 to C7;Chemical Synthesis;Halogenated Heterocycles;Heterocyclic Building Blocks;Pyridines;Pesticides intermediate
• Mol File: 1929-82-4.mol
• Article Data: 6

Chemical Properties

• Melting Point: 62-63°C
• Boiling Point: 136-138°C
• Flash Point: 100 °C
• Appearance: White/Powder
• Density: 1.8732 (rough estimate)
• Vapor Pressure: 0.0225mmHg at 25°C
• Refractive Index: 1.6000 (estimate)
• Storage Temp.: 0-6°C
• Solubility: Soluble in 10 mg/ml ethanol.
• PKA: -3.75±0.10(Predicted)
• Water Solubility: Insoluble.
• Merck: 14,6574
• BRN: 1618997
• CAS DataBase Reference: Nitrapyrin(CAS DataBase Reference)
• NIST Chemistry Reference: Nitrapyrin(1929-82-4)
• EPA Substance Registry System: Nitrapyrin(1929-82-4)

Safety Data

• Hazard Codes: Xn;N,Xi,N,Xn
• Statements: 22-51/53-36/37/38
• Safety Statements: 24-61-37/39-26
• RIDADR: UN 2811
• WGK Germany: 2
• RTECS: US7525000
• TSCA: Yes
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 1929-82-4(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 1929-82-4 differently. You can refer to the following data:
1. 2-?Chloro-?6-?(trichloromethyl)?pyridine is a nitrification inhibitor used to limit NO and N2O emissions from crops. Improves nitrogen use efficiency. Environmental toxin on US EPA Toxic Release Inventory list (TRI) list.
2. 2-Chloro-6-(trichloromethyl)pyridine is
3. Bactericide used to inhibit Nitrosomonas spp. from oxidizing ammonium ions in soil.
4. Fertilizer additive to control nitrification and prevent loss of soil nitrogen.

Chemical Properties

Crystals.

Physical properties

Colorless to white crystalline solid with a mild, sweet odor

General Description

Colorless crystals or off-white crystalline solid.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

Nitrapyrin is a base. Reacts exothermically with acids.

Hazard

Liver damage. Questionable carcinogen.

Fire Hazard

Flash point data for Nitrapyrin are not available. Nitrapyrin is probably combustible.

Flammability and Explosibility

Nonflammable

Agricultural Uses

Nitrapyrin, also called N serve, is a nitrification inhibitor

Safety Profile

Poison by ingestion. Moderately toxic by skin contact. Experimental reproductive effects. Mutation data reported. When heated to decomposition it emits very toxic fumes of Cland NOx.

Environmental Fate

Biological. 6-Chloropicolinic acid and carbon dioxide were reported as biodegradation products (Verschueren, 1983).Soil. Hydrolyzes in soil to 6-chloropyridine-2-carboxylic acid (Worthing and Hance, 1991).Photolytic. Photolysis of nitrapyrin in water yielded 6-chloropicolinic acid, 6-hydroxypicolinic acid and an unidentified polar material (Verschueren, 1983).Chemical/Physical. Emits toxic fumes of nitrogen oxides and chlorides when heated to decomposition (Sax and Lewis, 1987; Lewis, 1990).

InChI:InChI=1/C6H3Cl4N/c7-5-3-1-2-4(11-5)6(8,9)10/h1-3H

Synthetic route

α-picoline (109-06-8) → nitrapyrin (1929-82-4)

Conditions	Yield
With chlorine In water at 240℃; Temperature; Inert atmosphere;	89.4%
With chlorine at 160 - 195℃; Temperature; Concentration; Irradiation;	70.21%
With chlorine at 186.9 - 206.9℃;

picoline hydrochloride (14401-91-3) → 2-trichloromethylpyridine (4377-37-1) + 2,3,5-trichloropyridine (55934-01-5) + 2-(trichloromethyl)-3,5-dichloropyridine (1128-16-1) + 2,3-dichloro-6-(trichloromethyl)pyridine (51492-01-4) + nitrapyrin (1929-82-4) + 3,4,5-trichloro-2-trichloromethyl pyridine (1201-30-5)

Conditions	Yield
With chlorine at 150℃; for 2h; Product distribution; Kinetics; Irradiation; other temp.: 80, 90, 100, 120 deg. C; other reaction time: 2 to 45 h; reaction without irradiation; reaction in C4Cl6;

picoline hydrochloride (14401-91-3) → 2-trichloromethylpyridine (4377-37-1) + 2-(trichloromethyl)-5-chloropyridine (1197-03-1) + 2-(trichloromethyl)-3,5-dichloropyridine (1128-16-1) + 2,5-dichloro-6-(trichloromethyl)pyridine (1817-13-6) + nitrapyrin (1929-82-4) + 2-(trichloromethyl)-3-chloropyridine (1817-12-5)

Conditions	Yield
With chlorine at 185℃; for 21h; Product distribution; Rate constant; various temperatures, residence times and chlorine feed rates;	A 28.3 % Chromat. B 2.7 % Chromat. C n/a D 1.2 % Chromat. E 64.8 % Chromat. F 0.6 % Chromat.

α-picoline (109-06-8) + picoline hydrochloride (14401-91-3) → 2,5-dichloro-6-(trichloromethyl)pyridine (1817-13-6) + nitrapyrin (1929-82-4)

Conditions	Yield
Stage #1: α-picoline; picoline hydrochloride With chlorine at 195℃; for 36h; Industry scale; Stage #2: With chlorine at 170℃; for 8h; Product distribution / selectivity; UV-irradiation; Industry scale;

α-picoline (109-06-8) + picoline hydrochloride (14401-91-3) → 2-trichloromethylpyridine (4377-37-1) + 2,5-dichloro-6-(trichloromethyl)pyridine (1817-13-6) + nitrapyrin (1929-82-4)

Conditions	Yield
Stage #1: α-picoline; picoline hydrochloride With chlorine Industry scale; Stage #2: With chlorine Product distribution / selectivity; UV-irradiation; Industry scale;

α-picoline (109-06-8) + picoline hydrochloride (14401-91-3) → nitrapyrin (1929-82-4)

Conditions	Yield
Stage #1: α-picoline; picoline hydrochloride With chlorine at 195℃; Industry scale; Stage #2: With chlorine at 170℃; Product distribution / selectivity; UV-irradiation; Industry scale;

nitrapyrin (1929-82-4) + 4-fluoroaniline (371-40-4) → 6-chloro-N-(4-fluorophenyl)pyridin-2-amide (137640-94-9)

Conditions	Yield
With tetrabutylammonium tetrafluoroborate; oxygen In N,N-dimethyl-formamide at 25 - 30℃; Temperature; Reagent/catalyst; Solvent; Electrolysis;	97%
With hydrogenchloride; triethylamine In toluene	95%
Stage #1: nitrapyrin With sulfuric acid at 135℃; for 6h; Stage #2: 4-fluoroaniline With triethylamine In toluene at 20 - 120℃; for 1.75h;

nitrapyrin (1929-82-4) → 2-fluoro-6-(trifluoromethyl)pyridine

Conditions	Yield
With antimony(V) trichloride difluoride; SbF3Cl2; hydrogen fluoride at 120℃; under 3750.38 - 26252.6 Torr; for 6h; Temperature; Reagent/catalyst; Pressure; Autoclave; Inert atmosphere; Large scale;	96.7%
Multi-step reaction with 2 steps 1: iron(III) chloride; hydrogen fluoride / 22 h / 160 - 180 °C / 11251.1 - 18751.9 Torr 2: hydrogen fluoride / 22 h / 160 - 180 °C / 11251.1 - 18751.9 Torr View Scheme
With hydrogen fluoride for 15h; Time; Large scale;

nitrapyrin (1929-82-4) → 6-chloro-N-(4-fluorophenyl)pyridin-2-amide (137640-94-9)

Conditions	Yield
With sulfuric acid	95%
With sulfuric acid
With sulfuric acid

nitrapyrin (1929-82-4) + 3-Trifluoromethylphenol (98-17-9) → 2-(3-trifluoromethylphenoxy)-6-trichloromethylpyridine

Conditions	Yield
With sodium hydroxide In dimethyl sulfoxide; toluene at 150℃; for 8h;	95%

nitrapyrin (1929-82-4) + 6-chloro-2-chloromethylpyridine (78846-88-5) → 2-Chloro-6-(dichloromethyl)-pyridine (78152-53-1)

Conditions	Yield
	90.1%

nitrapyrin (1929-82-4) → 6-chloropicolinic acid (4684-94-0)

Conditions	Yield
With sulfuric acid; water at 100℃; for 8h;	90%
With sulfuric acid at 100℃; for 6h; Time;	90%

nitrapyrin (1929-82-4) + isopropyl alcohol (67-63-0) → isopropyl 2-chloro-pyrid-6-ylcarboxylate

Conditions	Yield
Stage #1: nitrapyrin With sulfuric acid at 135℃; for 6h; Stage #2: isopropyl alcohol at 20 - 65℃; for 0.5h;	88.4%

nitrapyrin (1929-82-4) → 2-Chloro-6-(dichloromethyl)-pyridine (78152-53-1)

Conditions	Yield
With chloroform; sodium hydroxide Ambient temperature;	88%
With chloroform; sodium hydroxide In dimethyl sulfoxide Rate constant; Mechanism; Ambient temperature; other solvents; accelerating and inhibiting additives added; other catalyst (PTC); in the presence of 40percent NaOD in D2O;

nitrapyrin (1929-82-4) → 2-chloro-6-trifluoromethylpyridine (39890-95-4)

Conditions	Yield
With hydrogen fluoride at 330℃;	80%

nitrapyrin (1929-82-4) + 1-t-Butoxycarbonylpiperazine (57260-71-6) → 4-tert-butoxycarbonyl-1-(6-chloropicolinoyl)piperazine

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In tetrahydrofuran at 70℃; Inert atmosphere;	19%

methanol (67-56-1) + nitrapyrin (1929-82-4) → 2-methoxy-6-trichloromethylpyridine

Conditions	Yield
With sodium 2.) reflux, 15 h; Yield given. Multistep reaction;

nitrapyrin (1929-82-4) → 2,3-dichloro-6-(trichloromethyl)pyridine (51492-01-4) + 2,5-dichloro-6-(trichloromethyl)pyridine (1817-13-6)

Conditions	Yield
With chlorine; ZnCl2, HCl, water and type L zeolite (EZ-200) mixed, dried and calcined at 200℃; under 25.8581 Torr; for 12.5h;
With tetrachloromethane; chlorine; Type L zeolite (TOSOH, HSZ-500KOA Lot#50KA1103) calcined at 200℃; under 25.8581 Torr; for 11h;
With chlorine; Cs-ion exchanged Type L zeolite at 200℃; under 25.8581 Torr; for 8h;

Nitroethane (79-24-3) + nitrapyrin (1929-82-4) + 4-fluoroaniline (371-40-4) → 6-chloro-N-(4-fluorophenyl)pyridin-2-amide (137640-94-9) + N-(4-fluorophenyl) 2-(3-trifluoromethylphenoxy)-pyrid-6-ylinecarboxamide

Conditions	Yield
With hydrogenchloride; sulfuric acid; triethylamine
With hydrogenchloride; sulfuric acid; triethylamine

nitrapyrin (1929-82-4) + iron(II) chloride → 2-Chloro-6-(dichloromethyl)-pyridine (78152-53-1)

Conditions	Yield
With hydrogenchloride In methanol; dichloromethane

nitrapyrin (1929-82-4) + methyl phosphite (96-36-6, 868-85-9) → 2-Chloro-6-(dichloromethyl)-pyridine (78152-53-1)

Conditions	Yield
With sodium hydroxide In 1-methyl-pyrrolidin-2-one; water

nitrapyrin (1929-82-4) → 2-fluoro-6-(trifluoromethyl)pyridine + 2-chloro-6-trifluoromethylpyridine (39890-95-4)

Conditions	Yield
With iron(III) chloride; hydrogen fluoride at 160 - 180℃; under 11251.1 - 18751.9 Torr; for 22h;	A 90.96 %Chromat. B 7.67 %Chromat.

nitrapyrin (1929-82-4) → 2-fluoro-6-(trifluoromethyl)pyridine + 2-chloro-6-(difluorochloromethyl)pyridine + 2-chloro-6-trifluoromethylpyridine (39890-95-4)

Conditions	Yield
With hydrogen fluoride at 180 - 200℃; under 15001.5 - 22502.3 Torr;	A 51.87 %Chromat. B 8.22 %Chromat. C 38.66 %Chromat.
With hydrogen fluoride at 150 - 175℃; for 12h;	A 40.28 %Chromat. B 10.22 %Chromat. C 48.49 %Chromat.

nitrapyrin (1929-82-4) → N-(4-fluorophenyl)-6-(3-trifluoromethylphenoxy)pyridine-2-carboxamide (137641-05-5)

Conditions	Yield
Multi-step reaction with 3 steps 1: sodium hydroxide / toluene; dimethyl sulfoxide / 8 h / 150 °C 2: iron(III) chloride; water / 1,2-dichloro-ethane / 25 h / Resolution of racemate 3: sodium hydroxide / 1,2-dichloro-ethane; water / 3 h / 15 - 20 °C / pH 8 View Scheme
Multi-step reaction with 4 steps 1: sodium hydroxide / toluene; dimethyl sulfoxide / 8 h / 150 °C 2: water; hydrogenchloride / 8 h / 120 °C 3: thionyl chloride / 4 h / Reflux 4: sodium hydroxide / 1,2-dichloro-ethane; water / 3 h / 15 - 20 °C / pH 8 View Scheme
Multi-step reaction with 4 steps 1: sulfuric acid; water / 8 h / 100 °C 2: potassium carbonate; copper(l) chloride / N,N-dimethyl-formamide / 6 h / 140 °C 3: pyridine; bis(trichloromethyl) carbonate / ethyl acetate / 2 h / 35 - 50 °C 4: triethylamine; bis(trichloromethyl) carbonate / dichloromethane / 3 h View Scheme
Multi-step reaction with 4 steps 1: sulfuric acid / 6 h / 100 °C 2: potassium carbonate; copper(l) chloride / N,N-dimethyl-formamide / 8 h / 140 °C 3: bis(trichloromethyl) carbonate; triethylamine / ethyl acetate / 2 h / 35 - 50 °C 4: bis(trichloromethyl) carbonate; triethylamine / dichloromethane / 3 h View Scheme

nitrapyrin (1929-82-4) → 2-(3-trifluoromethylphenoxy)-6-pyridinecarbonyl chloride (178108-94-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium hydroxide / toluene; dimethyl sulfoxide / 8 h / 150 °C 2: iron(III) chloride; water / 1,2-dichloro-ethane / 25 h / Resolution of racemate View Scheme
Multi-step reaction with 3 steps 1: sodium hydroxide / toluene; dimethyl sulfoxide / 8 h / 150 °C 2: water; hydrogenchloride / 8 h / 120 °C 3: thionyl chloride / 4 h / Reflux View Scheme
Multi-step reaction with 3 steps 1: sulfuric acid; water / 8 h / 100 °C 2: potassium carbonate; copper(l) chloride / N,N-dimethyl-formamide / 6 h / 140 °C 3: pyridine; bis(trichloromethyl) carbonate / ethyl acetate / 2 h / 35 - 50 °C View Scheme
Multi-step reaction with 3 steps 1: sulfuric acid / 6 h / 100 °C 2: potassium carbonate; copper(l) chloride / N,N-dimethyl-formamide / 8 h / 140 °C 3: bis(trichloromethyl) carbonate; triethylamine / ethyl acetate / 2 h / 35 - 50 °C View Scheme

nitrapyrin (1929-82-4) → 6-(3-α,α,α-trifluoromethylphenoxy)picolinic acid (137640-84-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium hydroxide / toluene; dimethyl sulfoxide / 8 h / 150 °C 2: water; hydrogenchloride / 8 h / 120 °C View Scheme
Multi-step reaction with 2 steps 1: sulfuric acid; water / 8 h / 100 °C 2: potassium carbonate; copper(l) chloride / N,N-dimethyl-formamide / 6 h / 140 °C View Scheme
Multi-step reaction with 2 steps 1: sulfuric acid / 6 h / 100 °C 2: potassium carbonate; copper(l) chloride / N,N-dimethyl-formamide / 8 h / 140 °C View Scheme

nitrapyrin (1929-82-4) → Nε-acryloyl-L-lysine-4-(6-chloropicolinoyl)piperazide*2TFA

Conditions

Yield

Multi-step reaction with 4 steps 1: caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; tris-(dibenzylideneacetone)dipalladium(0) / tetrahydrofuran / 70 °C / Inert atmosphere 2: trifluoroacetic acid / dichloromethane / 3 h 3: N-ethyl-N,N-diisopropylamine; benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate / tetrahydrofuran / 3 h 4: dichloromethane / 3 h View Scheme

nitrapyrin (1929-82-4) → Nα-phenylacetyl-Nε-acryloyl-L-lysine-4-(6-chloropicolinoyl)piperazide*TFA

Conditions

Yield

Multi-step reaction with 5 steps 1: caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; tris-(dibenzylideneacetone)dipalladium(0) / tetrahydrofuran / 70 °C / Inert atmosphere 2: trifluoroacetic acid / dichloromethane / 3 h 3: N-ethyl-N,N-diisopropylamine; benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate / tetrahydrofuran / 3 h 4: dichloromethane / 3 h 5: triethylamine / dichloromethane / 3 h View Scheme

nitrapyrin (1929-82-4) → 1-(6-chloropicolinoyl)piperazine

Conditions	Yield
Multi-step reaction with 2 steps 1: caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; tris-(dibenzylideneacetone)dipalladium(0) / tetrahydrofuran / 70 °C / Inert atmosphere 2: trifluoroacetic acid / dichloromethane / 3 h View Scheme

Upstream product

• 109-06-8 α-picoline 
• 14401-91-3 picoline hydrochloride 

Downstream Products

• 137640-94-9 6-chloro-N-(4-fluorophenyl)pyridin-2-amide 
• 78152-53-1 2-Chloro-6-(dichloromethyl)-pyridine 
• 94239-04-0 2-fluoro-6-(trifluoromethyl)pyridine 
• 39890-95-4 2-chloro-6-trifluoromethylpyridine 
• 4684-94-0 6-chloropicolinic acid 
• 137640-84-7 6-(3-α,α,α-trifluoromethylphenoxy)picolinic acid 
• 178108-94-6 6-(3-trifluoromethylphenoxy)pyridine-2-carbonyl chloride 
• 137641-05-5 N-(4-fluorophenyl)-6-(3-trifluoromethylphenoxy)pyridine-2-carboxamide 
• 220969-59-5 isopropyl 2-chloro-pyrid-6-ylcarboxylate 
• 51492-01-4 2,3-dichloro-6-(trichloromethyl)pyridine 
• 1817-13-6 2-(trichloromethyl)-3,6-dichloropyridine 

Relevant articles and documents

Standard enthalpy of formation of 2-chloro-6-(trichloromethyl)pyridine

The standard enthalpy of formation of 2-chloro-6-(trichloromethyl)pyridine(cr) was determined to be -(55.4 +/- 1.8) kJ * mol-1 at 298.15 K by rotating-bomb oxygen combustion calorimetry using paraffin oil as a combustion aid and As2O3(aq) as a reducing agent for Cl2 formed.Nitric acid and chlorometallic acids of noble metals present in the final bomb solution were analysed by ion-chromatographic and atomic-absorption spectrometric methods, respectively.The effect of catalytic pre-oxidation of As2O3(aq) was evaluated.The standard molar energy of combustion was calculated using a computation form derived by combining that for CHON compounds with that for CHOCl compounds.The modifications of the form are described.

Preparation method for 2-chloro-6-trichloromethylpyridine and catalyst thereof and preparation method for catalyst

The invention discloses a preparation method for 2-chloro-6-trichloromethylpyridine and a catalyst thereof and a preparation method for the catalyst, and belongs to the field of the 2-chloro-6-trichloromethylpyridine. The catalyst for preparing the 2-chloro-6-trichloromethylpyridine comprises a carrier and iron-containing pyridine chlorine salt ionic liquid, and the iron-containing pyridine chlorine salt ionic liquid is loaded on the carrier. The catalyst is capable of, through loading the iron-containing pyridine chlorine salt ionic liquid on the carrier, greatly improving a contact area of the catalyst of a reactant, and improving a preparation efficiency of the 2-chloro-6-trichloromethylpyridine. In addition, the invention further relates to the preparation method for the catalyst for preparing the above 2-chloro-6-trichloromethylpyridine and the preparation method for the 2-chloro-6-trichloromethylpyridine. Defects existing in a traditional 2-chloro-6-trichloromethylpyridine preparation method that a reaction temperature is overhigh, the yield of a finished product is low and the catalyst is not easy to regenerate because of deactivation are overcome.

MACROKINETIC RELATIONSHIPS OF HIGH-TEMPERATURE CHLORINATION OF 2-PICOLINE HYDROCHLORIDE

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