77182-82-2

Basic information

• Product Name: Glufosinate-ammonium
• Synonyms: DL-Phosphinothricin ammonium salt;FREE SAMPLE NCV GLUFOSINATE AMMONIUM;2-amino-4-(hydroxymethylphosphinyl)butanoicacidmonoammoniumsalt;2-amino-4-(hydroxymethylphosphinyl)-butanoicacimonoammoniumsalt;ammonium(3-amino-3-carboxypropyl)methylphosphinate;ammonium(dl-homoalanine-4-yl)methylphosphinate;Ammonium-DL-homoalanin-4-yl(methyl)phosphinate;ammoniumglufusinate
• CAS NO: 77182-82-2
• Molecular Formula: C₅H₁₂NO₄P*H₃N
• Molecular Weight: 215.19
• EINECS: 278-636-5
• Product Categories: Pharmaceutical intermediates;glutamine synthetase inhibitor;Amines;Phosphorylating and Phosphitylating Agents;NULL;inhibitor
• Mol File: 77182-82-2.mol

Chemical Properties

• Melting Point: 210°C
• Boiling Point: 519℃
• Flash Point: 100 °C
• Appearance: solid
• Density: 1.4 g/cm3
• Vapor Pressure: 3.61E-12mmHg at 25°C
• Storage Temp.: 0-6°C
• Solubility: Methanol (Slightly), Water (Soluble)
• PKA: 9.15[at 20 ℃]
• Water Solubility: Soluble in water
• Stability: Stable. Incompatible with strong oxidizing agents.
• Merck: 13,7425
• BRN: 8163399
• CAS DataBase Reference: Glufosinate-ammonium(CAS DataBase Reference)
• NIST Chemistry Reference: Glufosinate-ammonium(77182-82-2)
• EPA Substance Registry System: Glufosinate-ammonium(77182-82-2)

Safety Data

• Hazard Codes: Xn,T
• Statements: 22-48/20/22-20/21/22-63-60
• Safety Statements: 53-45-24/25
• RIDADR: 2588
• WGK Germany: 1
• RTECS: EK7713600
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 77182-82-2(Hazardous Substances Data)

Usage

Uses

Used in Agricultural Industry:
Glufosinate-ammonium is used as a herbicide for controlling a wide range of weeds after crop emergence or for total vegetation control on non-crop lands. It is particularly effective on crops that have been genetically engineered. Additionally, Glufosinate herbicides are used to desiccate crops before harvest.
Used in Organophosphorus Herbicides:
Glufosinate-ammonium is used as an organophosphorus herbicide, acting as a glutamine synthetase inhibitor. It is a non-selective contact herbicide with a certain suction effect, making it suitable for weeding in orchards, vineyards, and non-cultivated land.
Used in Weed Management:
Glufosinate-ammonium is used for the prevention and weeding of annual and perennial dicotyledonous weeds and sedges in potato fields. It targets weeds such as rat tail foxtail, crabgrass, barnyardgrass, foxtail, wild wheat, wild corn, cocksfoot, fescue, deschampsia flexuosa, hair grass, ryegrass, reed, bluegrass, wild oat, brome, cleavers, henbit, lamium, solanum nigrum, chickweed, quackgrass, bentgrass, calamagrostis grass, field forget-grass, bermuda grass, and amaranthus. The usage amount per hectare varies depending on the crops and weeds, ranging from 1-2 kg or more, such as for prevention and weeding of raspberry crops and fern in forests and alpine pastures, with an application rate of 1.5-20 kg/hm2.
Used as a Postemergence Herbicide and Desiccant:
Glufosinate-ammonium is also utilized as a postemergence herbicide and desiccant, providing effective weed control and aiding in the preparation of crops for harvest.

Organophosphorus herbicides

Glufosinate-ammonium, also known as glufosinate, is a non-selective foliar application of organic phosphorus herbicide, in 1979 first developed by the Federal Republic of Germany Hoechst (Hoechst) chemical synthesis company. Weeding mechanism of Glufosinate-ammonium is absorbed by the blade, having a part suction effect, can be transferred from the base of the blade to the ends, transferred less to other parts of the plant, is harmless for not unearthed shoots and seeds. Plants Glufosinate-ammonium metabolism is disordered in a short period after drug application, a strong cytotoxic agent Glufosinate-ammonium ion is accumulated in plants; poisoned the plant to die. While also severely inhibited photosynthesis, injured plants was yellowish white after lose of the green, after 2 to 5 days, turned yellow and died. After contacted with the soil, lost activity, it should only for spray of stem and leaf at postemergence. Applications: Glufosinate-ammonium is mainly used for destuctive weeding of orchards, vineyards, potato fields, nurseries, forests, pastures, ornamental shrubs and free arable, prevention and weeding of annual and perennial weeds such as foxtail, wild oats, crabgrass , barnyard grass, green foxtail, bluegrass, quackgrass, bermudagrass, bentgrass, reeds, fescue, etc. Also prevention and weeding of broadleaf weeds such as quinoa, amaranth, smartweed, chestnut, black nightshade, chickweed, purslane, cleavers, sonchus, thistle, field bindweed, dandelion, also have some effect on sedges and ferns. When broadleaf weeds in the beginning of growing season and grass weeds in tillering period, dosage of 0.7 to 1.2 kg/hectare was sprayed on weed populations, period of weed control is 4 to 6 weeks, administration again if necessary, can significantly extend the validity period. Potato field should be used in the pre-emergence, it can also be sprayed before harvest, killing and weeding ground stubble, so as to harvest. Prevention and weeding of ferns, dosage of per hectare is 1.5 to 2 kg. Usually alone, sometimes it can also be mixed with simajine, diuron or methylchloro phenoxyacetic acid, and so on. Figure 1 The chemical structural formula of Glufosinate-ammonium. The above information is edited by the lookchem of Liu Yujie.

Toxicity

Male rats acute oral LD50 is 2000 mg/kg, female rats is 1620 mg/kg; male mice acute oral LD50 is 431 mg/kg, female mice is 416 mg/kg; dog acute oral LD50 is 200~400 mg/kg. Male rats acute percutaneous LD50 is > 2000 mg/kg, female rats is 4000 mg/kg. No teratogenic and carcinogenic effects. Rainbow trout LC50 is 320mg/L (96h).

Production methods

The O, O-diethyl methyl phosphonate reacted with dibromoethane reaction, heated at 80 ℃ for 2 h to get BrCH2CH2P (O) (OC2H5) CH3, and then reacted with (C2H5O2C) 2CNa (NHCOCH3) at 85 ℃to get ( C2H5O2C) 2C (NHCOCH3) CH2CH2P (O) (OC2H5) CH3, which was refluxed with hydrochloric acid, the resulting compound reacted with 28% Glufosinate-ammonium hydroxide for 8 h at 60~70 ℃ to obtain Glufosinate-ammonium. In addition, synthesis of Glufosinate-ammonium included high-pressure catalytic synthesis method, low-temperature of targeting synthesis, using Strecker reaction and Mitchell addition process ,and so on. See "Pesticides" issue 9, 2002.

Acute toxicity

Oral-rat LD50: 1620 mg/kg; Oral-mouse LD50: 416 mg/kg.

Flammability hazard characteristics

Combustible; combustion produces toxic fumes of nitrogen oxides and sulfur oxides.

Storage characteristics

Treasury is ventilation, low-temperature and dry

Flammability and Explosibility

Notclassified

Trade name

BASTA?; DERRINGER?; FINALE?; HOE 00661?; HOE 03986?; HOE 39866?; IGNITE?; LIBERTY?; RELY?; REMOVE?; RUBOUT?; TOTAL?

Safety Profile

A poison by ingestion,subcutaneous, and intraperitoneal routes. Low toxicity byskin contact. Human systemic effects by ingestion: bloodpressure lowering, change in motor activity, coma,cyanosis. When heated to decomposition it emits toxicvapors of NO

InChI:InChI=1/C5H12NO4P.H3N/c1-11(9,10)3-2-4(6)5(7)8;/h4H,2-3,6H2,1H3,(H,7,8)(H,9,10);1H3

Synthetic route

glufosinate ammonium hydrochloride (59542-49-3) → ammonium glufosinate (77182-82-2)

Conditions	Yield
With L-serin; ammonia In water at 110℃; pH=8; pH-value; Reagent/catalyst;	98%
With ammonium hydroxide; ammonia In water at 70℃; pH=6 - 7;	94.9%
With ammonia In methanol; water at 20℃; pH=1; Solvent; Reagent/catalyst;	87 g

4-(hydroxymethylphosphinyl)-2-oxobutanoic acid (79778-02-2) → ammonium glufosinate (77182-82-2)

Conditions	Yield
Stage #1: 4-(hydroxymethylphosphinyl)-2-oxobutanoic acid With ruthenium-carbon composite; ammonia In methanol at 25 - 30℃; under 1500.15 Torr; for 10h; Sealed tube; Stage #2: With hydrogen at 50℃; under 4500.45 Torr; Temperature; Pressure;	97.8%
Stage #1: 4-(hydroxymethylphosphinyl)-2-oxobutanoic acid With ammonia at 20℃; under 3000.3 Torr; for 1h; Autoclave; Stage #2: With hydrogen at 50℃; under 30003 Torr; for 6h; Reagent/catalyst; Temperature; Pressure; Autoclave;	95%
Stage #1: 4-(hydroxymethylphosphinyl)-2-oxobutanoic acid With 5%-palladium/activated carbon; ammonia In methanol at 25℃; under 1500.15 Torr; for 4h; Stage #2: With hydrogen In methanol at 90℃; under 11251.1 Torr; for 6h;

2-amino-4-(methylethoxyphosphoryl)butyronitrile → ammonium glufosinate (77182-82-2)

Conditions	Yield
Stage #1: 2-amino-4-(methylethoxyphosphoryl)butyronitrile With hydrogenchloride In water at 104 - 110℃; for 3.5h; Large scale; Stage #2: With ammonium hydroxide at 45℃; for 1.5h; pH=7.5; pH-value; Large scale;	97.04%

DL-homoalanin-4-yl(methyl)phosphinic acid (51276-47-2) → ammonium glufosinate (77182-82-2)

Conditions	Yield
With ammonia In methanol; water at 20℃; for 1h; Solvent;	96%
With ammonia In ethanol; water at 20℃; for 1h; Solvent; Green chemistry;	96%
With ammonium carbonate In ethanol at 20℃; for 0.5h; Product distribution / selectivity;

C10H18NO4P → ammonium glufosinate (77182-82-2)

Conditions	Yield
With hydrogenchloride In water at 10℃; for 2h; Reflux;	92.7%
With hydrogenchloride In water at 10℃; for 2h; Reflux;	91.2%

glufosinate hydrochloride → ammonium glufosinate (77182-82-2)

Conditions	Yield
With ammonium hydroxide In methanol; water pH=9;	92.5%

C10H18NO4P → ammonium glufosinate (77182-82-2)

Conditions	Yield
With hydrogenchloride In water at 10℃; for 2h; Reflux;	90.5%
With hydrogenchloride In water at 10℃; for 2h; Reflux;	8.5 g

C13H24NO4P → ammonium glufosinate (77182-82-2)

Conditions	Yield
With hydrogenchloride In water at 10℃; for 2h; Reflux;	90.4%

C9H16NO4P → ammonium glufosinate (77182-82-2)

Conditions	Yield
With hydrogenchloride In water at 10℃; for 2h; Reflux;	90%

sodium cyanide (773837-37-9) + 3-oxopropylmethylphosphinic acid (121795-01-5) → ammonium glufosinate (77182-82-2)

Conditions	Yield
With ammonium hydroxide; ammonium chloride at 20 - 40℃; for 4h; Reagent/catalyst;	81.4%

C10H20NO6P → ammonium glufosinate (77182-82-2)

Conditions	Yield
Stage #1: C10H20NO6P With hydrogenchloride for 8h; Reflux; Stage #2: With ammonium hydroxide for 6h; pH=9; Reflux;	80.96%

(3-cyano-3-hydroxypropyl)(methyl)phosphinic acid → ammonium glufosinate (77182-82-2)

Conditions	Yield
With water; ammonium carbonate at 150℃; for 6h; Reagent/catalyst;	45.2 g

1-4-((ethoxy)(methyl)phosphoryl)butene (221319-78-4) → ammonium glufosinate (77182-82-2)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: copper dichloride; oxygen; palladium dichloride / water; acetonitrile / 6 h / 45 °C / 3750.38 Torr / Sealed tube 2.1: potassium permanganate; potassium hydroxide / water / 3.5 h / 0 - 50 °C 3.1: ammonia; ruthenium-carbon composite / methanol / 10 h / 25 - 30 °C / 1500.15 Torr / Sealed tube 3.2: 50 °C / 4500.45 Torr View Scheme

3-[n-butoxy(methyl)phosphoryl]-1-cyanopropyl acetate (172529-93-0) → ammonium glufosinate (77182-82-2)

Conditions	Yield
Stage #1: 3-[n-butoxy(methyl)phosphoryl]-1-cyanopropyl acetate With ammonia at 33 - 35℃; under 2625.26 Torr; for 1.6h; Autoclave; Inert atmosphere; Stage #2: With hydrogenchloride; water for 7h; Temperature; Cooling; Reflux;

ammonium glufosinate (77182-82-2) → Glufosinate-P-ammonium

Conditions	Yield
Stage #1: ammonium glufosinate With nickel(II) chloride hexahydrate; potassium hydroxide In methanol at 60℃; Stage #2: With hydrogenchloride In water at 100℃; for 3h; Reagent/catalyst; Solvent;	98%

Upstream product

• 51276-47-2 DL-homoalanin-4-yl(methyl)phosphinic acid 
• 59542-49-3 glufosinate ammonium hydrochloride 
• 79778-02-2 4-(hydroxymethylphosphinyl)-2-oxobutanoic acid 
• 221319-78-4 1-4-((ethoxy)(methyl)phosphoryl)butene 
• 773837-37-9 sodium cyanide 
• 121795-01-5 3-oxopropylmethylphosphinic acid 
• 172529-93-0 3-[n-butoxy(methyl)phosphoryl]-1-cyanopropyl acetate 

Downstream Products

• 82785-28-2 L-glufosinate ammonium 
• 73634-73-8 2-acetylamino-4-(hydroxy(methyl)phosphinyl)butanoic acid 

Relevant articles and documents

Method for preparing phosphorus-containing a-aminonitriles

The present invention relates primarily to processes conducted in a continuously operated reactor for preparing particular phosphorus-containing α-aminonitriles of the formulae (Ia) and (Ib) defined hereinafter from corresponding phosphorus-containing cyanohydrin esters and to the use thereof for preparation of glufosinate or of glufosinate salts. The present invention further relates to a process for producing glufosinate/glufosinate salts.

Synthesis method of glufosinate-ammonium

The invention relates to the field of pesticides, in particular to a synthesis method of glufosinate-ammonium. The synthesis method of glufosinate-ammonium comprises the following steps: reacting a mixed aqueous solution of a hydantoin derivative, volatile alkali and a catalyst under 1.0-2.5 MPa, and after the reaction is finished, carrying out post-treatment to obtain glufosinate-ammonium, wherein the catalyst is a guanidine compound. The synthesis method of glufosinate-ammonium provided by the invention jumps out of the thought of separating glufosinate-ammonium from inorganic salt in the prior art, creatively adopts the mutual cooperation of volatile alkali and the catalyst (guanidine compound), and hydrolyzes the hydantoin derivative under the specific pressure of 1.0-2.5 MPa, so that the hydantoin compound is thoroughly hydrolyzed, the yield of glufosinate-ammonium is improved, meanwhile, the reaction time is shortened, acid-base neutralization is not needed after the reaction is finished, inorganic salt is not generated, generation of the inorganic salt in the glufosinate-ammonium preparation process is fundamentally eradicated, three wastes are not generated, the yield of glufosinate-ammonium is high, and industrial popularization is easy.

Preparation method of glufosinate-ammonium

The invention discloses a preparation method of glufosinate-ammonium. According to the method, methyl phosphine dichloride is used as a raw material, and reacts with acrolein under the action of acetic anhydride to obtain an unsaturated phosphine-containing heterocyclic ring represented by a formula I; a hydrolysis reaction is performed to obtain a phosphine aldehyde intermediate represented by aformula II; the phosphine aldehyde intermediate is subjected to a strecker reaction to obtain an amino nitrile intermediate; and the amino nitrile intermediate is sequentially subjected to a hydrolysis reaction and a salifying reaction to obtain glufosinate-ammonium. According to the invention, the preparation method is short in technological process, and particularly can directly obtain the phosphine aldehyde intermediate without diethyl methylphosphite, so that the production cost of glufosinate-ammonium can be greatly reduced, and the further commercial popularization of glufosinate-ammonium is facilitated; and the method has good environmental friendliness, avoids the wastewater generated by the Grignard reaction in the traditional method, and also has no great potential safety hazard.

Process for preparing phosphorus-containing alpha-aminonitriles

The present invention relates primarily to processes for preparing particular phosphorus-containing α-aminonitriles of the formulae (Ia) and (Ib) defined hereinafter from corresponding phosphorus-containing cyanohydrin esters and to the use thereof for preparation of glufosinate or of glufosinate salts. The present invention further relates to a process for preparing glufosinate or glufosinate salts.

Method for synthesizing glufosinate ammonium salt

The invention discloses a method for synthesizing a glufosinate ammonium salt. The method comprises the following steps that (1) methyldiethoxyphosphine and n-butanol are used as raw materials to produce an intermediate I by hydrolysis and transesterification; (2) the intermediate I is subjected to a free radical addition reaction with acrolein cyanohydrin acetate to form an intermediate II; (3) the intermediate II is subjected to an aminolysis reaction with ammonia gas to form a mixture of an intermediate III and an intermediate IV; (4) the intermediate III and the intermediate IV are subjected to acid hydrolysis with hydrochloric acid to form an intermediate V; and (5) the intermediate V is neutralized, purified and crystallized to obtain the glufosinate ammonium salt. The method does not need to use toxic raw materials, avoids the large-scale use of ammonia water and ammonium chloride, not only greatly reduces the safety hazard, but also reduces the quantity of by-products and the amount of waste water generated, and the environmental protection risk is greatly reduced; and the purification process is simple, the product content and the yield coefficient are obviously increased,and the method is suitable for industrial scale production.

Synthetic method for glufosinate ammonium

The invention relates to a synthetic method for glufosinate ammonium. The synthetic method comprises the following steps: single-bromine substitution, amination, amino protection, chlorination ring opening, Arbuzov reaction and acidizing hydrolysis ammoniation; the single-bromine substitution means triggering alpha-site single-bromine substitution betweengamma-butyrolactone I and bromine under theexistence of catalyst and performing reduced pressure distillation, thereby acquiring a pure intermediate II alpha-bromine-gamma-butyrolactone; phosphorus tribromide is served as the catalyst; amination means triggering amination reaction between alpha-bromine-gamma-butyrolactone II and ammonium hydroxide, and then adding hydrochloric acid and reflowing, thereby acquiring an intermediate IIIalpha-amino-gamma-butyrolactone hydrochloride. The invention has the beneficial effects: 1) low-costgamma-butyrolactone is taken as a raw material, is subjected to single-bromine substitution with bromineand then is subjected to amination reaction with ammonium hydroxide; the adopted raw materials are low-cost and easily acquired; reaction conditions are mild; operation is simple and convenient; safety is high; amplifying production is feasible; reaction yield is high; product purity is high; cost is greatly lowered; the synthetic method is suitable for industrial production.

Glufosinate ammonium salt intermediate and synthesis method of glufosinate ammonium salt

The invention provides a glufosinate ammonium salt intermediate and a synthesis method of glufosinate ammonium salt. The glufosinate ammonium salt intermediate is a compound III (wherein a formula IIIis shown in the description); the synthesis method comprises the following steps: step (1): enabling a compound I (wherein a formula I is shown in the description) and oxygen gas to react and synthesize a compound II (wherein a compound II is shown in the description) in a Pd (II) catalysis system under the reaction conditions that the temperature is 20 to 60 DEG C and the pressure is 0.4 to 0.7MPa; step (2): dissolving the compound II (wherein the compound II is shown in the description) into an alkaline water solution and reacting with an oxidant at 0 to 50 DEG C; then carrying out acidification to synthesize the compound III (wherein the formula III is shown in the description), wherein R is selected from one of C1 to C5 alkyl; then dissolving the compound III (wherein the formula IIIis shown in the description) into a solvent and adding a catalyst to react with ammonia gas and hydrogen gas in sequence, so as to prepare the glufosinate ammonium salt, i.e., a compound IV (wherein aformula IV is shown in the description). Compared with a traditional glufosinate ammonium synthesis technology, the method provided by the invention has the advantages of no utilization of highly toxic cyanide and Grignard reaction, relatively moderate reaction conditions, easiness for controlling, short steps, high yield and low cost and is suitable for industrial production.

Grass-ammonium phosphine separation and purification method

The invention belongs to the field of pesticide production and particularly relates to a glufosinate separation and purification method. According to the method, the separation and purification is started when a glufosinate hydrochloride reaction solution in the steps of distilling the glufosinate hydrochloride reaction solution under reduced pressure to remove dilute hydrochloric acid, adding ammonia water to adjust the pH to maximally produce ammonium chloride, distilling under reduced pressure to remove water, adding a flotation solvent for dispersion, placing the material into a chute at specific temperature and speed, performing flotation separation according to the difference in the proportion of a principal component and subsidiary salt, removing the solvent, dissolving the material in aqueous methanol to remove trace ammonium chloride, filling ammonia gas to adjust the pH value to 8, performing centrifugation and drying to obtain a final product. The glufosinate separation and purification method uses a flotation method for separating the principal component glufosinate and an intermediate of the principal component from the subsidiary salt ammonium chloride and the aqueous methanol for purification and is high in yield, good in purity, simple in process, low in cost and is suitable for industrial production.

Glufosinate ammonium preparation method

The invention relates to a glufosinate ammonium preparation method which includes the steps: (1) taking a compound 3 as a raw material, and performing reaction for the compound 3 and a compound 5 at the temperature ranging from 10 DEG C to 80 DEG C under the actions of alkali; (2) reacting a compound 6 at the temperature ranging from 50 DEG C to 120 DEG C under the actions of acid to obtain a compound 7. The structural formula of the compound 3 is as shown in the specification, the structural formula of the compound 5 is as shown in the specification, the structural formula of the compound 6 is as shown in the specification, the structural formula of the compound 7 is as shown in the specification, wherein R1 is alkyl, the carbon number of the alkyl is 1-5, R2 is alkyl, and the carbon number of the alkyl is 1-3. The preparation method is simple in step, low in cost and suitable for industrial production, cannot generate high-salinity wastewater and more meets environment-friendly requirements, and both the yield and the content of final products are high.

Method for synthesis of glufosinate

The invention relates to a method for synthesis of glufosinate. The method comprises that (1) a compound 4 as a raw material and a compound 5 undergo a reaction at a temperature of 10 to 80 DEG C under the action of a base to obtain a compound 6, and (2) the compound 6 undergoes a reaction under the action of an acid at a temperature of 50 to 120 DEG C to produce a compound 7, wherein the compound 4 has a structural formula shown in the description, the compound 5 has a structural formula shown in the description, the compound 6 has a structural formula shown in the description, the compound 7 has a structural formula shown in the description, R1 represents an alkyl group having 1 to 5 carbon atoms and R2 represents an alkyl group having 1 to 3 carbon atoms. The method has simple processes and a low cost, does not produce high salt wastewater, satisfies environmental protection requirements, is suitable for industrial production, and has high yield and content of the finished product.