151-56-4 Usage
Description
Ethyleneimine is a colourless liquid with an ammonia-like smell or pungent odour. It is
highly flammable and reacts with a wide variety of materials. Ethyleneimine is used
in polymerisation products, as a monomer for polyethyleneimine and as a comonomer
for polymers, for example, with ethylenediamine. Polymerised ethyleneimine is used in
paper, textile chemicals, adhesive binders, petroleum, refining chemicals, fuels, lubricants,
coating resins, varnishes, lacquers, agricultural chemicals, cosmetics, ion-exchange
resins, photographic chemicals, colloid flocculants, and surfactants. Ethyleneimine readily
polymerises, and it behaves like a secondary amine. Ethyleneimine is highly caustic,
attacking materials such as cork, rubber, many plastics, metals, and glass except those
without carbonate or borax. It polymerises explosively on contact with silver, aluminium,
or acid. The activity of ethyleneimine is similar to that of nitrogen and sulphur mustards.
Ethyleneimine is used as an intermediate in the production of triethylenemelamine.
Chemical Properties
Different sources of media describe the Chemical Properties of 151-56-4 differently. You can refer to the following data:
1. colourless liquid with an ammonia-like smell
2. Ethyleneimine is a colorless liquid with an ammonia-like smell or pungent odor. It is
highly flammable and reacts with a wide variety of materials. Ethyleneimine is used in
polymerization products, as a monomer for polyethyleneimin, and as a comonomer for
polymers, e.g., with ethylenediamine. Polymerized ethylenimine is used in paper, textile
chemicals, adhesive binders, petroleum, refi ning chemicals, fuels, lubricants, coating resins,
varnishes, lacquers, agricultural chemicals, cosmetics, ion-exchange resins, photographic
chemicals, colloid fl occulants, and surfactants.
Ethyleneimine readily polymerizes, and it behaves like a secondary amine. Ethyleneimine
is highly caustic, attacking materials such as cork, rubber, many plastics, metals, and glas except those without carbonate or borax. It polymerizes explosively on contact with silver,
aluminum, or acid. The activity of ethyleneimine is similar to that of nitrogen and sulfur mustards.
Ethyleneimine is used as an intermediate in the production of triethylenemelamine.
Polymerized ethyleneimine is used in paper, textile chemicals, adhesive binders, petroleum,
refi ning chemicals, fuels, lubricants, coating resins, varnishes, lacquers, agricultural chemicals,
cosmetics, ion-exchange resins, photographic chemicals, colloid fl occulants, and surfactants
3. Ethyleneimine is a colorless volatile liquid with
an ammoniacal odor.
4. The strained three-membered ring structure of ethyleneimine readily undergoes ring-opening reactions, which are catalyzed by acids and occur at moderate temperatures. Ethyleneimine is easily polymerized at elevated temperatures in the presence of catalytic amounts of acid. Reactions with ammonia and primary orsecondary amines in the presence of catalytic amounts of acids yield ethylenediamines; reactions with carboxylic acids yield 2-aminoethyl esters.Ethyleneimine is also a highly reactive secondary amine, and undergoes a large number of reactions under neutral or basic conditions which yield products with the three-membered ring intact. Addition reactions occur with acyl halides, alkyl and substituted alkyl halides, aryl halides, and other halogen-containing compounds. Ethyleneimine forms adducts with aldehydes, ketones, and olefinic compounds (Ham 1978).
Physical properties
Clear, colorless, very flammable liquid with a very strong ammonia odor. Odor threshold
concentration is 1.5 ppm (quoted, Amoore and Hautala, 1983).
Uses
Different sources of media describe the Uses of 151-56-4 differently. You can refer to the following data:
1. Ethylenimine is used in the manufacture oftriethylenemelamine and other amines.
2. Ethyleneimine is used to manufacture triethylenemelamine
and is used in its polymeric form in paper and textile
chemicals, adhesive binders, petroleum-refining chemicals,
fuels and lubricants, coating resins, varnishes, lacquers,
agricultural chemicals, cosmetics, ion-exchange resins, photographic
chemicals, colloid flocculants, and surfactants.
3. In the manufacture of triethylenemelamine.
Production Methods
Industrial quantities are made with monoethanolamine via a two-step chemical dehydration process using sulphuric acid and sodium hydroxide, or by reacting 1,2-dichloroethane with ammonia. The U.S. production in 1978 was over 1500 metric tons (Ham 1978).
General Description
A clear colorless liquid with an ammonia-like odor. Flash point 12°F. Less dense than water. Flammable over a wide range of vapor-air concentrations. Vapors irritate the skin, eyes, nose, and throat. May be toxic by prolonged inhalation, skin absorption, or ingestion. Carcinogenic. Vapors heavier than air. May polymerize exothermically if heated or contaminated. If the polymerization takes place inside a container, the container may rupture violently.
Air & Water Reactions
Highly flammable. Soluble in water.
Reactivity Profile
ETHYLENEIMINE vapors are not inhibited and may form polymers in vents or flame arresters, resulting in stopping of the vents. Produces toxic oxides of nitrogen during combustion. Reacts with sodium hypochlorite and other chlorinating agents to give the explosive compound 1-chloroazidine. Decomposes if heated under pressure. or else hazardous polymerization may occur. Incompatible with silver or aluminum, which induce polymerization May polymerize explosively upon contact with acids. Polymerization is catalyzed by carbon dioxide [EPA, 1998].
Hazard
Corrosive, absorbed by skin, causes tumors;
exposure should be minimized; a carcinogen. Dangerous fire and explosion hazard, flammable limits
in air 3.6–46%. Toxic by skin absorption; possible
carcinogen.
Health Hazard
Different sources of media describe the Health Hazard of 151-56-4 differently. You can refer to the following data:
1. Ethyleneimine is classified as extremely toxic with a probable oral lethal dose of 5-50 mg/kg which is approximately 7 drops to 1 teaspoonful for a 70 kg (150 lb.) person. Ethyleneimine gives inadequate warning when over-exposure is by inhalation or skin absorption. It is a severe blistering agent, causing third degree chemical burns of the skin. Also, it has a corrosive effect on mucous membranes and may cause scarring of the esophagus. It is corrosive to eye tissue and may cause permanent corneal opacity and conjunctival scarring. Severe exposure may result in overwhelming pulmonary edema. Renal damage has been described. Hemorrhagic congestion of all internal organs has been observed.
2. Exposures to ethyleneimine cause adverse health effects and poisoning. Ingestion/swallowing,
inhalation, or absorption through exposures to skin cause severe irritation, blisters,
severe deep burns, and effects of sensitization. Ethyleninime is corrosive to the eye tissue
and may cause permanent corneal opacity and conjunctival scarring, severe respiratory
tract irritation, and effects of infl ammation in workers. Ethyleneimine is a severe blistering
agent, causing third degree chemical burns of the skin. The symptoms of toxicity include,
but are not limited to, cough, dizziness, headache, labored breathing, nausea, vomiting,
tearing and burning of the eyes, sore throat, nasal secretion, bronchitis, shortness of breath,
laryngeal edema, pronounced changes of the trachea and bronchi of lungs. Ethyleneimine
with its corrosive effects cause injury to the mucous membranes and acute oral exposure
may cause scarring of the esophagus in humans. The onset of symptoms and health effects
caused by ethyleneimine depends on exposure concentration.
3. Ethylenimine is a highly poisonous com pound and a severe irritant to the skin, eyes,and mucous membranes. A 20–25% aqueoussolution on contact with the eyes can causecorneal opacity and loss of vision. Skin con tact with the pure liquid or its concentratedsolution can produce severe burns and skinsensitization.Ethylenimine is highly toxic by all routesof exposure. Inhalation of its vapors cancause eye, nose, and throat irritations anddifficulty in breathing. The toxic symptomsnoted from repeated exposures include chestcongestion, delayed lung injury, vomiting,hemorrhage, and kidney damage. An 8-hourexposure to 100 ppm in air proved fatal torabbits. The symptoms from acute oral toxic ity in humans may include nausea, vomiting,dizziness, headache, and pulmonary edema.Chronic toxic effects may result in kidneyand liver damage. The acute oral LD50 valuein rats was 15 mg/kg. Ethylenimine is alsoabsorbed through the skin, exhibiting poi soning effects similar to those of acute oraltoxicity.It exhibited reproductive toxicity in ani mals, indicating paternal effects and specificdevelopmental abnormalities in the centralnervous system, eyes, and ears. Ethylenimineis a mutagen, testing positive in the histi dine reversion–Ames test as well as in thein vitro cytogenetics–human lymphocyte,Drosophila melanogaster–reciprocal translo cation, Saccharomyces cerevisiae gene con version, and other mutagenic tests. Animalstudies show sufficient evidence of carcino genicity. It may cause cancers in the lungsand liver.
4. Ethylenimine is highly toxic by all exposure routes. Airborne exposure causes conjunctivitis, respiratory tract irritation, edema, and albuminuria (Weightman and Hoyle 1964), with possible damage to liver and kidneys; vomiting and other CNS effects may occur at high exposures. Dermal contact to ethylenimineproduces severe irritation, with lesions which are slow to heal. Ethylenimines are also skin sensitizers (Garabrant 1985; Cofield et al 1985). There are no reports which indicate potential reproductive effects or increased risk for cancer in humans exposed to ethylenimine.
Fire Hazard
Irritating vapors are generated when heated. Vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back. May polymerize in fires with evolution of heat and container rupture. Runoff to sewer may create fire or explosion hazard. Ethyleneimine vapors are not inhibited and may form polymers in vents or flame arresters, resulting in stopping of the vents. Toxic oxides of nitrogen are produced during combustion. Upon treatment with sodium hypochlorite, Ethyleneimine gives off the explosive compound 1-chloroazidine. Avoid acids, sodium hypochlorite. If heated under pressure, instability may result. Hazardous polymerization may occur. Avoid contact with silver or aluminum. Explosive polymerization may occur upon contact with acids. Polymerization is catalyzed by carbon dioxide.
Flammability and Explosibility
Highlyflammable
Chemical Reactivity
Reactivity with Water: Mild reaction, non-hazardous; Reactivity with Common Materials: Contact with silver or aluminum may cause polymerization; Stability During Transport: Stable unless heated under pressure; Neutralizing Agents for Acids and Caustics: Flush with water; Polymerization: Explosive polymerization can occur when in contact with acids; Inhibitor of Polymerization: None used.
Industrial uses
Approximately 50% of ethylenimine produced in the U.S. is polymerized to polyethyleneimine, used as a flocculant in water treatment, and as a wet-strength additive in the textile and paper industries. Polyethylenimine is also used in various adhesives and coatings and to laminate plastic films to paper, other cellulose materials, and metal foils for making cartons in the food industry. The adhesion properties of acrylic latex paints are improved by reaction of acid groups with ethylenimine. Ethylenimines are utilized in the textile industry to improve durability, crease resistance, flame resistance, and dyeing properties. Other uses are found in ion-exchange resin synthesis, in electroplating, as a rocket propellant binder, as a lubricating oil dispersant, and as a hardening agent in the preparation of photographic films. Ethylenimine is used in the manufacture of triethylene melamine, a cancer chemotherapy drug; various ethylenimines are used as insect chemosterilant agents for pest control (Ham 1978).
Safety Profile
Confirmed carcinogen
with experimental carcinogenic,
neoplastigenic, tumorigenic, and teratogenic
data. Other experimental reproductive
effects. Poison by ingestion, skin contact,
inhalation, and intraperitoneal routes. Human mutation data reported. A skin, mucous
membrane, and severe eye irritant. An
allergc sensitizer of skin. Causes opaque cornea, keratoconus, and necrosis of cornea
(experimentally). Has been known to cause
severe human eye injury. Drinking of
carbonated beverages is recommended as an
antidote to ths material in stomach.
A very dangerous fire and explosion
hazard when exposed to heat, flame, or
oxidzers. Reacts violently with acids,
aluminum chloride + substituted anilines,
acetic acid, acetic anhydride, acrolein, acrylic
acid, allyl chloride, CS2, Cl2, chlorosulfonic
acid, epichlorohydrin, glyoxal, HCl, HF,
HNO3, oleum, P-propiolactone, Ag, NaOCl,
H2SO4, vinyl acetate. Reacts with chlorinating agents (e.g., sodum hypochlorite
solution) to form the explosive 1
chloroaziridine. Reacts with silver or its
alloys to form explosive silver derivatives.
Dangerous; heat and/or the presence of
catalytically active metals or chloride ions
can cause a violent exothermic reaction. To
fight fire, use alcohol foam, CO2, dry
chemical. When heated to decomposition it
emits acrid smoke and irritating fumes.
Potential Exposure
Ethyleneimine is used in production
of binding agents; formation of plastics; and improving
paper strength; in many organic syntheses; as an intermediate and monomer for fuel oil and lubricating refining. The
polymerization products, polyethyleneimines, are used as
auxiliaries in the paper industry and as flocculation aids in
the clarification of effluents. It is also used in the textile
industry for increasing wet strength, flame-, water-, shrinkproofing, and stiffening
Carcinogenicity
The carcinogenicity of ethyleneimine
was evaluated in two strains of mice, and both gave
positive results. Groups of 18 male and 18 female
mice of B6C3F1 or B6AKR strains were treated orally
(initially by gavage, then in the diet) from age 7 days through
77–78 weeks. The time-weighted average (TWA) dose was
about 1.8 mg/kg/day. The incidence of hepatomas and lung
adenomas was significantly elevated in both strains and
sexes. In B6C3F1 mice, the incidence of hepatomas
and pulmonary adenomas was 15/17 and 15/17 in males
and 11/15 and 15/15 females, respectively. In the B6AKR strain, hepatomas and adenomas occurred in 9/16 and 12/16
males and in 2/11 and 10/11 females, respectively. In the
control groups, hepatomas were 8/79 and 0/87 in male and
female B6C3F1 mice and 5/90 and 1/82 in male and female
B6AKR mice. The respective incidence of pulmonary adenomas
was 5/79, 3/87, 10/90, and 3/82. The incidence of
hepatomas and pulmonary adenomas (reported as combined
tumors) was significantly (p<0.01) elevated.
Environmental fate
Photolytic. The vacuum UV photolysis (λ = 147 nm) and γ radiolysis of ethylenimine resulted
in the formation of acetylene, methane, ethane, ethylene, hydrogen cyanide, methyl radicals, and
hydrogen (Scala and Salomon, 1976). Photolysis of ethylenimine vapor at krypton and xenon lines
yielded ethylene, ethane, methane, acetylene, propane, butane, hydrogen, ammonia, and ethyleneimino
radicals (Iwasaki et al., 1973).
Chemical/Physical. Polymerizes easily (Windholz et al., 1983). Hydrolyzes in water forming
ethanolamine (HSDB, 1989). The estimated hydrolysis half-life in water at 25 °C and pH 7 is 154
d (Mabey and Mill, 1978).
Metabolism
When male Dow-Wistar rats were injected intraperitoneally with [14C]-ethylenimine (80mug), approximately half of the dose was excreted in the urine (Wright and Rowe 1967). The major portion of the radioactivity in the urine consisted of unidentified products, although a small amount was excreted unchanged. A small portion, 3-5%, was expired as 14C02, and 1-3% was expired as a volatile, basic material, probably ethylenimine, during 24 h. Significant amounts of radioactivity were accumulated in liver, intestines, cecum, spleen, and kidneys. After 24 h, tissue radioactivity became constant and essentially unavailable for further metabolism. The aziridine ring of drugs is readily cleaved by microsomal enzymes, possibly with intermediate formation of an N-oxide (Oelschlager and Al Shaik 1985).
Shipping
UN1185 Ethyleneimine, stabilized, Hazard class:
6.1; Labels: 6.1-Poison Inhalation Hazard, 3-Flammable
liquid, Inhalation Hazard Zone A. PGI
Purification Methods
Redistil it in an Ar or N2 atmosphere in a fume hood, and store it over KOH in sealed bottles in a refrigerator. Commercial aziridine has been dried over sodium and distilled from the metal through an efficient column before use [Jackson & Edwards J Am Chem Soc 83 355 1961, Wenker J Am Chem Soc 57 2328 1935]. It is a weaker base than Me2NH (pK2 5 10.87) but is caustic to the skin. It should not be inhaled, causes inflammation of the eyes, nose and throat, and one may become sensitized to it. It is soluble in H2O, has an ammoniacal smell and reacts with CO2. Pure aziridine is comparatively stable but polymerises in the presence of traces of H2O and is occasionally explosive in the presence of acids. CO2 is sufficiently acidic to cause polymerisation (forms linear polymers) which is not free radical promoted. It is stable in the presence of bases. The violet 2:1 Cu complex crystallises from EtOH containing a few drops of aziridine and adding Et2O, and has m 142o(dec). The picrate has m 142o. [O'Rourke et al. J Am Chem Soc 78 2159 1956.] It has also been dried over BaO and has been distilled from sodium under nitrogen. [Allen et al. Org Synth Coll Vol IV 433 1963, Beilstein 20 III/IV 1.] TOXIC.
Toxicity evaluation
Ethyleneimine is an extremely reactive alkylating agent that
undergoes ring-opening reactions with cellular nucleophiles.
Incompatibilities
May form explosive mixture with air.
Ethyleneimine is a medium strong base. Contact with
acids, aqueous acid conditions, oxidizers, aluminum, or
carbon dioxide may cause explosive polymerization.
Explosive silver derivatives may be formed with silver
alloys e.g., silver solder). Self-reactive with heat or atmospheric carbon dioxide. May accumulate static electrical
charges, and may cause ignition of its vapors. Attacks
rubber, coatings, plastics, and chemically active metals.
Ethyleneimine vapors are not inhibited and may form
polymers in vents or flame arresters, resulting in stopping
of the vents.
Precautions
During use of ethyleninime, students and occupational workers should wear protective
equipment, such as gloves, safety glasses, and should have good ventilation. Ethyleninime
should be handled as a carcinogen. Ethyleninime vapor/air mixtures are explosive and
pose a risk of fi re and explosion on contact with acid(s), oxidants.
Check Digit Verification of cas no
The CAS Registry Mumber 151-56-4 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,5 and 1 respectively; the second part has 2 digits, 5 and 6 respectively.
Calculate Digit Verification of CAS Registry Number 151-56:
(5*1)+(4*5)+(3*1)+(2*5)+(1*6)=44
44 % 10 = 4
So 151-56-4 is a valid CAS Registry Number.
InChI:InChI=1/C2H3N/c1-2-3/h3H,1H2
151-56-4Relevant articles and documents
Inverse-Electron-Demand Palladium-Catalyzed Asymmetric [4+2] Cycloadditions Enabled by Chiral P,S-Ligand and Hydrogen Bonding
Wang, Ya-Ni,Xiong, Qin,Lu, Liang-Qiu,Zhang, Qun-Liang,Wang, Ying,Lan, Yu,Xiao, Wen-Jing
, p. 11013 - 11017 (2019)
Catalytic asymmetric cycloadditions of ambident Pd-containing dipolar species with nucleophilic dipolarophiles, namely, inverse-electron-demand cycloadditions, are challenging and underdeveloped. Possibly, the inherent linear selectivity of Pd-catalyzed intermolecular allylations and the lack of efficient chiral ligands are responsible for this limitation. Herein, two cycloadditions of such intermediates with deconjugated butenolides and azlactones were accomplished by using a novel chiral hybrid P,S-ligand and hydrogen bonding. By doing so, highly functionalized, optically active dihydroquinol-2-ones were produced with generally high reaction efficiencies and selectivities. Preliminary DFT calculations were performed to explain the high enantio- and diastereoselectivities.
Thermogravimetric Analyzer(TG)-Gas Chromatography(GC)/Mass Spectrometry(MS) and Pyrolytic Studies of 1,6-Bis(2-oxooxazolidin-3-ylcarbonylamino)hexane
Shimasaki, Choichiro,Murai, Atsuko,Sakai, Yukiko,Tsukumirichi, Eiichi
, p. 1009 - 1012 (1988)
1,6-Bis(2-oxooxazolidin-3-ylcarbonylamino)hexane (1) was prepared from 2-oxazolidinone and hexamethylenediisocyanurate using triethylenediamine as a catalyst in benzene.A TG effluent gas is collected in a cold trap and then directly injected into a GC for separation, the MS for unequivocal identification.The 13 effluent compounds from the thermal degradation of 1 were identified.
Vapor-phase transport as a novel route to hyperbranched polyamine-oxide hybrid materials
Chaikittisilp, Watcharop,Didas, Stephanie A.,Kim, Hyung-Ju,Jones, Christopher W.
, p. 613 - 622 (2013)
A new method to prepare hyperbranched polyamine-oxide hybrid materials by means of a vapor-phase transport is developed. In this method, hybrid materials having hyperbranched amine polymers covalently bound to an oxide support are formed by exposing the oxide support to the vapor of small nitrogen-containing heterocyclic monomers, in contrast to the conventional liquid-phase method, in which the support is dispersed in an organic solution containing monomer species. The aziridine and azetidine monomers are polymerized on the surface of the oxide supports (i.e., silica and alumina), resulting in poly(ethylenimine) or poly(propylenimine) chains attached to the porous solid support. The results suggest that the hybrid materials can be prepared over a wide range of preparation conditions with organic contents comparable to or even higher than those obtained from the standard liquid-phase method. It is demonstrated that supports with more acidity result in the hybrid materials with higher organic content. Interestingly, the resulting supported polyamines have lower molecular weights than the previously reported materials prepared by the liquid-phase method. It is anticipated that the vapor-phase synthesis can be applied for the efficient introduction of polyamines into structural forms of supports such as fibers, membranes, and monoliths, for which the liquid-phase method may be inappropriate or inefficient.
Organocatalyzed cycloaddition of carbon dioxide to aziridines
Wu, Yichen,Liu, Guosheng
, p. 6450 - 6452 (2011)
An efficient and simple process for the fixation of carbon dioxide (CO 2) to aziridine for the synthesis of 2-oxazolidinone by using DBN as catalyst, LiI as an additive under atmospheric pressure was developed. This chemical fixation of CO2 could also be carried out at room temperature with prolonged reaction time.
The Reactions of NH Radicals with Ethylene and Propene in the Liquid Phase
Kitamura, Takashi,Tsunashima, Shigeru,Sato, Shin
, p. 55 - 59 (1981)
The photolysis of hydrogen azide was studied in liquid ethylene, propene, and the mixture with ethane at the temperature of Dry Ice-methanol.The products observed were aziridine (0.18), ammonia (0.16), and nitrogen (1.0) from the ethylene solution and 2-methylaziridine (0.33), allylamine (0.12), ammonia (0.17), and nitrogen (1.0) from the propene solution.The values in parentheses show the yields relative to that of nitrogen.The relative yields were independent of the concentration of hydrogen azide in the range of 0.8-8*10-2 mol dm-3.The reaction of NH(a1Δ) radicals with olefin consists of three processes: the addition to double bond, the insertion into the C-H bond, and the deactivation to the 3Σ- state.The branching ratios and the relative rate constants of the reactions of NH(a1Δ) radicals with ethylene, propene, and ethane were estimated.
Effect of Distortion on the Hydrolytic Reactivity of Amides. 2. N-Pyramidalization: Decomposition of N-Benzoylaziridines in Aqueous Media
Slebocka-Tilk, H.,Brown, R. S.
, p. 805 - 808 (1987)
The decomposition of para-substituted N-benzoylaziridines (H, OCH3, NO2, Br) in buffered aqueous media is studied at 25 deg C as a function of pH in order to assess the effect of N-pyramidalization on the hydrolytic reactivity of the amide bond.Overall, the reaction shows three dominant terms: OH- and H2O attack on the neutral form and H2O attack on the protonated form of the amide.In base, the exclusive reaction is rate-limiting and irreversible attack of OH- on the C=O unit leading to normal hydrolytic products.This is shown by the first-order dependence on -> from pH 8 to 14 of the hydrolysis rate and by the fact that ca. 50percent 18O-enriched amide recovered from the hydrolysis medium as a function of time shows no 18O loss.Relative to N,N-dimethylbenzamide (kOH-25 deg C = 6.0 * 10-6 M-1 s-1), N-benzoylaziridine is ca. 200 000-fold more susceptible to OH- attack (kOH-25 deg C = 1.1 M-1 s-1).The kOH- terms follow a ?ρ relationship with ρ = 1.68.In acid, the products are not the expected hydrolytic ones of benzoic acid and aziridine.Rather, exclusive ring opening occurs to give p-X-C6H4C(=O)NHCH2CH2OX.In acetate buffers, product analysis by 1H NMR indicates that the ring-opened material consists of alcohol and acetate (X = H and C(=O)CH3).
Method for synthesizing fluopyram
-
Paragraph 0018; 0033-0036; 0040-0041, (2021/09/26)
The invention provides a method for synthesizing fluopyram, which uses commercially available 2 - bromoethylamine hydrobromide as a starting raw material, generates cyclopropylamine by self nucleophilic substitution reaction under basic conditions, and then reacts with o-trifluorobenzoyl chloride to prepare the key intermediate cyclopropylamine -1 -(2 - (trifluoromethyl) phenyl) methyl ketone. 2,3 -dichloro -5 -trifluoromethylpyridine was reacted with cyclopropylamine -1 -based (2 - (trifluoromethyl) phenyl) methyl ketone after the action of alkyllithium to give fluopyram. 1st-step and 2nd-step reactions are one-pot reaction, the reaction yield is high, the synthesis process is simple, the product purity is high, and the method has huge application value.
Barium complexes with crown-ether-functionalised amidinate and iminoanilide ligands for the hydrophosphination of vinylarenes
Le Coz, Erwann,Roueindeji, Hanieh,Roisnel, Thierry,Dorcet, Vincent,Carpentier, Jean-Francois,Sarazin, Yann
supporting information, p. 9173 - 9180 (2019/07/04)
The detailed multistep syntheses of two nitrogen-based sterically congested iminoanilidine and amidine proligands bearing a tethered 15-member aza-ether-crown macrocycle, namely {I^Acrown}H and {Amcrown}H, are reported. These proligands react with [Ba{N(SiMe2H)2}2·(thf)n] to generate the heteroleptic barium complexes [{I^Acrown}BaN(SiMe2H)2] (5) and [{Amcrown}BaN(SiMe2H)2] (6) in high yields. These complexes exhibit high coordination numbers (resp. eight and seven) and are in addition stabilised by mild Ba?H-Si interactions. Unusually for oxophilic elements such as barium, the amidinate ligand in 6 is only η1-coordinated. Complexes 5 and 6 mediate the intermolecular hydrophosphination of styrene with primary (PhPH2) and secondary (HPPh2) phosphines. Their catalytic performance compares favourably with those of other barium precatalysts for these reactions. During the course of the hydrophosphination of styrene with HPPh2 catalysed by 5, the phosphide complex [{I^Acrown}BaPPh2] (7) could be intercepted and crystallographically characterised.