The metabolism and disposition of tri-p-cresyl phosphate (TPCP) were studied in the rat after a single oral administration of [methyl-(14)C] TPCP.... The major urinary metabolites were p-hydroxybenzoic acid, di-p-cresyl phosphate (DCP), and p-cresyl p-carboxyphenyl phosphate (1coDCP). The biliary metabolites were DCP, 1coDCP, and the oxidized triesters, di-p-cresyl p-carboxyphenyl phosphate (1coTPCP), and p-cresyl di-p-carboxyphenyl phosphate (2coTPCP). The main fecal metabolite was TPCP, and the others were similar to those of bile. Following oral administration, TPCP was absorbed from the intestine, distributed to the fatty tissues, and moderately metabolized to a variety of products of oxidation and dearylation of TPCP, which were then excreted in the urine, feces, bile, and expired air. The intestinal microflora appeared to play an important role in degrading biliary metabolites to (14)CO2 through the enterohepatic circulation in rats.
Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Tri-Ortho-Cresyl Phosphate (TOCP) and Related Compounds/
Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . /Tri-Ortho-Cresyl Phosphate (TOCP) and Related Compounds/
Persons to be employed or work in which there is a danger of exposure to tricresyl phosphates should receive a pre-employment medical examination; persons with cardiorenal or nervous disorders should be /protected/. /Tricresyl phosphates/
/SIGNS AND SYMPTOMS/... CHRONIC TOXICITY OF TRITOLYL PHOSPHATE, WHEN THERE WAS SIMULTANEOUS INHALATION & CUTANEOUS ABSORPTION. MAIN SYMPTOMS WERE HYPERHYDROSIS, HYPOTENSION, GENERAL FATIGUE, AFFECTIVE IRRITABILITY, & PARESTHESIA IN LIMBS. /ISOMERIC MIXT/
The distribution and excretion of (14)C-labeled isomerically pure tri-o-, tri-m- and tri-p-cresyl phosphates has been examined in F344/N rats... Groups of male rats were administered /0.5, tri-m and tri-p only/, 2, 20, or 200 mg/kg of the respective (14)C-labeled isomerically pure tricresyl phosphate in corn oil by gavage, or 20 mg/kg was administered intravenously. All three compounds were well absorbed after oral administration; however, the pattern of excretion of each of the three triesters was different. Tri-o-cresyl phosphate was excreted primarily in the urine with approximately 70% of the label appearing in urine and 20% in feces within 24 hours for all three dose levels administered. Tri-m-cresyl phosphate was excreted primarily in the feces at all four dose levels administered (0.5, 2, 20, or 200 mg/kg); however, as the dose increased the percentage excreted in the feces also increased and that excreted in urine decreased. Tri-p-cresyl phosphate exhibited yet a different excretion pattern; at low doses (0.5 or 2 mg/kg) the primary route of excretion was the urine, whereas at higher doses (20 or 200 mg/kg) the primary route of excretion was the feces. Evaluation of biliary excretion following intravenous administration indicated that after administration of 2 or 20 mg/kg tri-o-cresyl phosphate or tri-m-cresyl phosphate approximately 40% to 60% of the label was excreted in the bile within the first 6 hours. However, tri-p-cresyl phosphate exhibited a dose dependent increase which represented an approximate doubling of biliary excretion between the 2 mg/kg and 20 mg/kg doses. The percentage of administered label appearing in feces was less than that excreted in bile for all three triesters, suggesting that substantial enterohepatic recycling occurs. Within 3 days after administration essentially 100% of the label of all three isomers had been excreted. All three isomers were rapidly distributed to muscle and liver and then redistributed to adipose tissue and skin; however, the parent compounds were rapidly cleared with no tendency to bioaccumulate in specific organs or tissues. Within 12 hours of dermal administration of a 50 mg/kg dose of (14)C-tri-o-cresyl phosphate to the intrascapular region of cats, 73% of the radioactivity had disappeared from the site of application, and within 24 hours it reached its maximum concentration in all organs and tissues examined... Within 10 days after administration, 28% of the applied radio activity had been excreted in the urine and 20% in the feces. Although studies of skin absorption have not been conducted with other isomeric tricresyl phosphate esters, the similarity of structure and physical properties (solubility, etc.) make it likely that these compounds are also absorbed through the skin.
来源:Hazardous Substances Data Bank (HSDB)
吸收、分配和排泄
... 三苯基磷酸盐 ... 人体难以吸收（消化途径和通过皮肤）。
... TRI-PARATOLYL PHOSPHATE ... ABSORBED WITH DIFFICULTY BY HUMAN BODY (DIGESTION ROUTE & VIA SKIN).
... /TRITOLYL PHOSPHATE/ CAN NORMALLY PENETRATE INTO BODY BY INGESTION OF LIQ OR SPRAY IN ATMOSPHERE & BY CUTANEOUS ABSORPTION. ... IT SEEMS THAT ONLY PHOSPHATES CONTAINING ORTHO-SUBSTITUTED PHENOL ARE ABSORBED THROUGH SKIN. /ISOMERIC MIXT/
The metabolism and disposition of tri-p-cresyl phosphate (TPCP) were studied in the rat after a single oral administration of [methyl-(14)C] TPCP. At a dosage of 7.8 mg/kg, most of the administered radioactivity was excreted in the urine (41%) and feces (44%) in 7 days. For 3 days, the expiratory excretion as (14)CO2 amounted to 18% of the radioactivity, but was reduced to 3% by treatment of the animal with neomycin. In separate rats, the biliary excretion amounted to 28% of the dose in 24 hr. At a dose of 89.6 mg/kg, the radioactivity was excreted in urine (12%) and feces (77%) in 7 days, and the expired air (6%) in 3 days. At 24, 72, and 168 hr after oral administration, the concentration of radioactivity was relatively high in adipose tissue, liver, and kidney...Following oral administration, TPCP was absorbed from the intestine, distributed to the fatty tissues, and moderately metabolized to a variety of products of oxidation and dearylation of TPCP, which were then excreted in the urine, feces, bile, and expired air. The intestinal microflora appeared to play an important role in degrading biliary metabolites to (14)CO2 through the enterohepatic circulation in rats.
申请人：Commissariat a L'Energie Atomique et aux Energies Alternatives
公开号：US20170240485A1
公开（公告）日：2017-08-24
The invention relates to a method for (I) producing a carboxylic ester of formula (I). Said method comprises the steps of: a) bringing an organosilane/borane of formula Si or B into contact with CO
2
, in the presence of a catalyst and an electrophilic compound of formula (III), the groups R
1
, R
2
, R
3
, R
4
, R
5
, Y, and M′ being as defined in claim 1; and optionally b) recovering the compound of formula (I) produced.
Palladium-Catalyzed C(sp<sup>2</sup>)–N Bond Cross-Coupling with Triaryl Phosphates
作者：Zicong Chen、Xiangmeng Chen、Chau Ming So
DOI：10.1021/acs.joc.9b00703
日期：2019.5.17
The first general palladium-catalyzed amination of aryl phosphates is described. The combination of MorDalPhos with [Pd(π-cinnamyl)Cl]2 enables the amination of electron-rich, electron-neutral, and electron-poor aryl phosphates with a board range of aromatic, aliphatic, and heterocyclic amines. Common functional groups such as ether, keto, ester, and nitrile show an excellent compatibility in this
Industrially important triaryl phosphites, traditionally prepared from PCl3, have been synthesized by a diphenyl diselenide-catalyzed one-step procedure involving white phosphorus and phenols, which provides a halogen- and transition metal-free way to these compounds. Subsequent oxidation of triaryl phosphites produces triaryl phosphates and triaryl thiophosphates. Phosphorotrithioates are also prepared
Compositions are described which comprise
(a) a lubricant, subject to oxidative or thermal degradation, and
(b) at least one compound of formula I
wherein
R⁵, R⁶, R⁷ and R⁸ are independently hydrogen, alkenyl of 3 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 15 carbon atoms, -CN, -NO⁶, halogen, -ORψ, -NR¼R½, -SR¾, -COOR| and -CONR⁵⁴R⁵⁵ where Rψ, R¼, R½, R¾, R|, R⁵⁴ and R⁵⁵ are independently hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, aryl of 6 to 10 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or aralkyl of 7 to 15 carbon atoms.
Some of the compounds of formula one are novel.
The invention comprises lubricating compositions and hydraulic fluids containing N,N′-diaryl-o-phenylenediamine compounds that impart good levels of oxidation inhibition in the lubricants and hydraulic fluids. The invention further comprises a method of making N,N′-diaryl-o-phenylenediamine compounds.
